Fluorovinyl derivative compound, liquid crystal composition, and liquid crystal display device

ABSTRACT

There are herein disclosed a fluorovinyl derivative compound represented by the general formula (1) and having characteristics of a liquid crystal, a liquid crystal composition, and a liquid crystal display device formed by using this composition:                    
     wherein R 1  is an alkyl group having 1 to 18 carbon atoms, and a methylene group in the alkyl group may be substituted by an oxygen atom, a sulfur atom, —CH═CH— or —C≡C— and a hydrogen atom in the alkyl group may be substituted a halogen atom or a cyano group; rings A, B and C are each 1,4-cyclohexylene, 1,4-phenylene or the like in which a hydrogen atom in the ring may be substituted by a halogen atom; Z 1 , Z 2  and Z 3  are each a single bond, —CH 2 CH 2 —, —CH═CH—, —C≡C—, —CH 2 O—, —OCH 2 —, —(CH 2 ) 4 —, —(CH 2 ) 3 —O—, —O—(CH 2 ) 3 —, —(CH 2 ) 2 —CH═CH—, —CH═CH—(CH 2 ) 2 —, —CF 2 O—, —OCF 2 —, —CR 2 ═CH—, —CH═CR 2 — or —CF═CF—, and R 2  is an alkyl group having 1 to 5 carbon atoms; X is a hydrogen atom or a fluorine atom; p and q are each 0 or 1; and m is an integer of 0 to 5.

TECHNICAL FIELD

The present invention relates to a novel liquid crystal compound usefulas a liquid crystal display material. More specifically, it relates to anovel liquid crystal compound having suitable characteristics such assteep threshold properties, a low viscosity, a good compatibility withanother liquid crystal compound and a proper optical anisotropy value, anovel liquid crystal composition and a liquid crystal display deviceformed by using this compound.

BACKGROUND ART

Heretofore, liquid crystal compounds are important as compounds for usein the manufacture of displays of various electrooptic devices. Amongthe various liquid crystal compounds, compounds having an alkenyl groupas a side chain are suitable as the liquid crystal compounds for STN,and the various compounds having the alkenyl group have been synthesizedand evaluated, and some of these compounds have been put to practicaluse. For example, the following compounds (s-1) to (s-3) have beendisclosed in Mol. Cryst. Liq. Cryst., 122, p. 241 (1985) and JapanesePatent Application Laid-open No. 83136/1986, the following compounds(s-4) and (s-5) have been revealed in Japanese Patent Application No.92740/1994, and the following compounds (s-6) and (s-7) have beendisclosed in DE19520246Al.

However, the above liquid crystal compounds are poor in steep thresholdproperties which are required for the liquid crystal compounds for STN,and all of them have strong smectogenic properties, so that if a liquidcrystal composition containing a large amount of such a compound isprepared, there is a problem that the compatibility of such a liquidcrystal compound with another liquid crystal compound in the liquidcrystal composition at a low temperature is low. In particular, thecompounds (s-4) to (s-7) have each a high viscosity, and so there is alarge problem that a response speed of the liquid crystal compositionusing such a compound is low.

Compounds (s-8) and (s-9) in which a fluorine atom is directly bonded toa double bond have been disclosed in Japanese Patent NationalPublication (Kohyo) No. 500343/1994, and a compound (s-10) has beenrevealed in Japanese Patent National Publication (Kohyo) No.502627/1992. However, the compounds (s-8) and (s-9) are extremely poorin chemical stability (particularly, heat stability), and therefore theuse of these compounds is practically impossible. Moreover, in JapanesePatent National Publication (Kohyo) No. 502627/1992, there have beendisclosed compounds alone in which a terminal group is limited to apolar group such as a halogen atom.

DISCLOSURE OF THE INVENTION

The present inventors have intensively investigated to solve the aboveproblems, and as a result, it has been found that a fluorovinylderivative compound represented by the general formula (1) has

(1) an extremely high elastic constant ratio (K₃₃/K₁₁),

(2) a very low viscosity,

(3) a wide nematic phase temperature range,

(4) a high chemical stability, and

(5) a proper optical anisotropy value and dielectric anisotropy value.

Furthermore, it has also been found that a liquid crystal composition inwhich the compound of the general formula (1) is used has

(1) steep threshold voltage properties,

(2) a feature that a response time is short,

(3) a wide operation temperature range (a good compatibility withanother liquid crystal compound),

(4) a chemical stability, and

(5) a feature that a drive power is low.

In addition, it has also been confirmed that the compound of the generalformula (1) is suitable for the preparation of the liquid crystalcomposition for STN (super-twisted nematic) which is most extensivelyused at present. In consequence, the present invention has now beencompleted.

Therefore, an object of the present invention is to provide a novelfluorovinyl derivative compound suitable for a display material, and aliquid crystal composition in which this compound is used. Inparticular, the object of the present invention is to provide a novelliquid crystal compound having steep threshold properties, a lowviscosity, a good compatibility with another liquid crystal compound anda proper optical anisotropy value and dielectric anisotropy value, anovel liquid crystal composition and a liquid crystal display deviceformed by using this compound.

The present invention which can achieve the above object is constitutedas follows.

The 1st aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1)

wherein R₁ is an alkyl group having 1 to 18 carbon atoms, and amethylene group in the alkyl group may be substituted by an oxygen atom,a sulfur atom, —CH═CH— or —C≡C— and a hydrogen atom in the alkyl groupmay be substituted by a halogen atom or a cyano group;

rings A, B and C are each independently 1,4-cyclohexylene,1,4-cyclohexenylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl,pyridine-2,5-diyl or pyrimidine-2,5-diyl in which a hydrogen atom in thering may be substituted by a halogen atom;

Z₁, Z₂ and Z₃ are each independently a single bond, —CH₂CH₂—, —CH═CH—,—CH₂O—, —OCH₂—, —(CH₂)₄—, —(CH₂)₃—O—, —O—(CH₂)₃—, —(CH₂)₂—CH═CH—,—CH═CH—(CH₂)₂—, —CF₂O—, —OCF₂—, —CR₂═CH—, —CH═CR₂— or —CF═CF—, and R₂ isan alkyl group having 1 to 5 carbon atoms;

X is a hydrogen atom or a fluorine atom; p and q are each independently0 or 1; and m is an integer of 0 to 5;

each element in the formula may be substituted by its isotope; but

except (1) a compound in which p is 0, q is 0, Z₃ is the single bond,—CH₂CH₂—, —CH₂O— or —OCH₂—, and the ring C is 1,4-cyclohexylene or1,4-phenylene, and (2) a compound in which p is 0, q is 1, Z₂ and Z₃ areeach the single bond, the ring B is 1,4-phenylene, and the ring C is1,4-cyclohexylene or 1,4-phenylene.

The 2nd aspect of the present invention is directed to the fluorovinylderivative compound according to the 1st aspect of the present inventionwherein at least one of Z₁, Z₂ and Z₃ is —CH═CH—, —(CH₂)₃—O—,—O—(CH₂)₃—, —(CH₂)₂—CH═CH—, —CH═CH—(CH₂)₂—, —CF₂O—, —OCF₂—, —CR₂═CH—,—CH═CR₂— or —CF═CF—; and R₂ is an alkyl group having 1 to 5 carbonatoms.

The 3rd aspect of the present invention is directed to the fluorovinylderivative compound according to the 1st aspect of the present inventionwherein at least one of Z₁, Z₂ and Z₃ is —CH═CH—, —(CH₂)₂—CH═CH—,—CH═CH—(CH₂)₂— or —CF═CF—.

The 4th aspect of the present invention is directed to the fluorovinylderivative compound according to the 1st aspect of the present inventionwherein at least one of Z₁, Z₂ and Z₃ is —(CH₂)₃—O—, —O——(CH₂)₃—, —CF₂O—or —OCF₂—.

The 5th aspect of the present invention is directed to the fluorovinylderivative compound according to the 1st aspect of the present inventionwherein at least one of Z₁, Z₂ and Z₃ is —CR₂═CH— or —CH═CR₂—; and R₂ isan alkyl group having 1 to 5 carbon atoms.

The 6th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-1)

wherein R₁, X and m are as defined in the 1st aspect of the presentinvention; Z₁, Z₂ and Z₃ are each independently a single bond, —CH₂CH₂—,—CH₂O—, —OCH₂— or —(CH₂)₄—; and rings A, B and C are each independently1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom in the ringmay be substituted by a halogen atom.

The 7th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-2)

wherein R₁, X and m are as defined in the 1st aspect of the presentinvention; r and s are each independently 0 or 1; and L₁, L₂, L₃ and L₄are each independently a hydrogen atom or a fluorine atom.

Typical examples of the compound represented by the general formula(1-2) include compounds of the following formulae:

wherein R₁, m and L₁ to L₄ are as defined above.

The 8th aspect of the present invention is directed to the fluorovinylderivative compound according to the 7th aspect of the present inventionwherein r+s is 1 or 0.

The 9th aspect of the present invention is directed to the fluorovinylderivative compound according to the 7th aspect of the present inventionwherein r+s is 2.

The 10th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-3)

wherein R₁, X, m, L₁, L₂, L₃ and L₄ are as defined in the 7th aspect ofthe present invention; Z₂ and Z₃ are each independently a single bond,—CH₂CH₂—, —CH₂O—, —OCH₂— or —(CH₂)₄—, and Z₂ and Z₃ are notsimultaneously the single bonds; and a ring C is 1,4-cyclohexylene or1,4-phenylene in which a hydrogen atom in the ring may be substituted bya halogen atom.

Typical examples of the compound represented by the general formula(1-3) include compounds of the following formulae:

wherein R₁, m and L₁ to L₈ are as defined above.

The 11th aspect of the present invention is directed to the fluorovinylderivative compound according to the 10th aspect of the presentinvention wherein the ring C is 1,4-cyclohexylene.

The 12th aspect of the present invention is directed to the fluorovinylderivative compound according to the 10th aspect of the presentinvention wherein the ring C is 1,4-phenylene in which a hydrogen atomin the ring may be substituted by a halogen atom.

The 13th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-1-1)

wherein R₁, X and m are as defined in the 1st aspect of the presentinvention; and L₁ to L₈ are each independently a hydrogen atom or afluorine atom.

Typical examples of the compound represented by the general formula(1-1-1) include compounds of the following formulae:

wherein R₁, m and L₁ to L₈ are as defined above.

The 14th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-1-2)

wherein R₁, X and m are as defined in the 1st aspect of the presentinvention; L₁ to L₁₂ are each independently a hydrogen atom or afluorine atom; and r is 0 or 1.

Typical examples of the compound represented by the general formula(1-1-2) include compounds of the following formulae:

wherein R₁, m and L₁ to L₁₂ are as defined above.

The 15th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-1-3)

wherein R₁, X and m are as defined in the 1st aspect of the presentinvention; L₁ to L₈ are each independently a hydrogen atom or a fluorineatom; and r is 0 or 1.

Typical examples of the compound represented by the general formula(1-1-3) include compounds of the following formulae:

wherein R₁, m and L₁ to L₈ are as defined above.

The 16th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-4-1)

wherein R₁, X and m are as defined in the 1st aspect of the presentinvention; and the ring C is 1,4-cyclohexylene or 1,4-phenylene in whicha hydrogen atom in the ring may be substituted by a halogen atom.

Typical examples of the compound represented by the general formula(1-4-1) include compounds of the following formulae:

wherein R₁, m and L₁ to L₄ are as defined above.

The 17th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-4-2)

wherein R₁, X and m are as defined in the 1st aspect of the presentinvention; and the rings B and C are each 1,4-cyclohexylene or1,4-phenylene in which a hydrogen atom in the ring may be substituted bya halogen atom.

Typical examples of the compound represented by the general formula(1-4-2) include compounds of the following formulae:

wherein R₁ ₁ m and L₁ to L5 are as defined above.

The 18th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-4-3)

wherein R₁, X and m are as defined in the 1st aspect of the presentinvention; and the rings B and C are each 4-cyclohexylene or1,4-phenylene in which a hydrogen atom in the ring may be substituted bya halogen atom.

Typical examples of the compound represented by the general formula(1-4-3) include compounds of the following formulae:

wherein R₁, m and L₁ to L8 are as defined above.

The 19th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-4-4)

wherein R₁, X, m, Z₁ and p are as defined in the 1st aspect of thepresent invention; and the ring A is 1,4-cyclohexylene or 1,4-phenylenein which a hydrogen atom in the ring may be substituted by a halogenatom.

Typical examples of the compound represented by the general formula(1-4-4) include compounds of the following formulae:

wherein R₁, m and L₁ to L₄ are as defined above.

The 20th aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-4-5)

wherein R₁, X, m, Z₁ and p are as defined in the 1st aspect of thepresent invention; the ring A is 1,4-cyclohexylene or 1,4-phenylene inwhich a hydrogen atom in the ring may be substituted by a halogen atom;and Z₂ is —CF₂O— or —OCF₂—.

Typical examples of the compound represented by the general formula(1-4-5) include compounds of the following formulae:

wherein R₁, m and L₁ to L₄ are as defined above.

The 21st aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-4-6)

wherein R₁, X, m, Z₁ Z₃, p and q are as defined in the 1st aspect of thepresent invention; the rings A, B and C are each 1,4-cyclohexylene or1,4-phenylene in which a hydrogen atom in the ring may be substituted bya halogen atom; and R₂ is an alkyl group having 1 to 5 carbon atoms.

Typical examples of the compound represented by the general formula(1-4-6) include compounds of the following formulae:

wherein R₁₁ R₂₁ m and L₁ to L₁₂ are as defined above.

The 22nd aspect of the present invention is directed to a fluorovinylderivative compound represented by the general formula (1-4-7)

wherein R₁, X, m, Z₁, Z₃, p and q are as defined in the 1st aspect ofthe present invention; the rings A, B and C are each 1,4-cyclohexyleneor 1,4-phenylene in which a hydrogen atom in the ring may be substitutedby a halogen atom; and R₂ is an alkyl group having 1 to 5 carbon atoms.

Typical examples of the compound represented by the general formula(1-4-7) include compounds of the following formulae:

wherein R₁, R₂, m and L₁ to L₁₂ are as defined above.

The 23rd aspect of the present invention is directed to a liquid crystalcomposition which contains at least one of the liquid crystal compoundsdescribed in the 1st aspect to the 22nd aspect of the present invention.

The 24th aspect of the present invention is directed to a liquid crystalcomposition which contains, as a first component, at least one of theliquid crystal compounds described in the 1st aspect to the 22nd aspectof the present invention, and as a second component, at least onecompound selected from the group consisting compounds of the generalformulae (2), (3) and (4)

wherein R₃ is an alkyl group having 1 to 10 carbon atoms, and anoptional unadjacent methylene group in the alkyl group may besubstituted by an oxygen atom or —CH═CH—, and an optional hydrogen atomin the alkyl group may be substituted by a fluorine atom; Y₁ is afluorine atom, a chlorine atom, OCF₃, OCF₂H, CF₃, CF₂H, CFH₂, OCF₂CF₂Hor OCF₂CFHCF₃; L₁₃ and L₁₄ are each independently a hydrogen atom or afluorine atom; Z₄ and Z₅ are each independently a 1,2-ethylene group, a1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, —CH═CH— or a single bond; aring D is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylenein which a hydrogen atom may be substituted by a halogen atom; a ring Eis trans-1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom maybe substituted by a fluorine atom; and an atom in each formula may besubstituted by its isotope.

The 25th aspect of the present invention is directed to a liquid crystalcomposition which contains, as a first component, at least one of theliquid crystal compounds described in the 1st aspect to the 22nd aspectof the present invention, and as a second component, at least onecompound selected from the group consisting compounds of the generalformulae (5) and (6)

wherein R₄ and R₅ are each independently an alkyl group having 1 to 10carbon atoms, and an optional unadjacent methylene group in the alkylgroup may be substituted by an oxygen atom or —CH═CH—, and an optionalhydrogen atom in the alkyl group may be substituted by a fluorine atom;Y₂ is a —CN group or —C≡C—CN; a ring F is trans-1,4-cyclohexylene,1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; a ring G istrans-1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl in which ahydrogen atom may be substituted by a fluorine atom; a ring M istrans-1,4-cyclohexylene or 1,4-phenylene; Z₆ is a 1,2-ethylene group,—COO— or a covalent bond; L₁₅, L₁₆ and L₁₇ are each independently ahydrogen atom or a fluorine atom; b, c and d are each independently 0 or1; and an atom in each formula may be substituted by its isotope.

The 26th aspect of the present invention is directed to a liquid crystalcomposition which contains at least one of the liquid crystal compoundsdescribed in the 1st aspect to the 22nd aspect of the present inventionas a first component, at least one compound selected from the groupconsisting compounds of the general formulae (2), (3) and (4) as asecond component, and at least one compound selected from the groupconsisting compounds of the general formulae (7), (8) and (9) as a thirdcomponent

wherein R₆ and R₇ is each independently an alkyl group having 1 to 10carbon atoms, and an optional unadjacent methylene group in the alkylgroup may be substituted by an oxygen atom or —CH═CH—, and an optionalhydrogen atom in the alkyl group may be substituted by a fluorine atom;rings I, J and K are each independently trans-1,4-cyclohexylene,pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may besubstituted by a fluorine atom; Z₇ and Z₈ are each independently —C≡C—,—COO—, —CH₂CH₂—, —CH═CH— or a single bond; and an atom in each formulamay be substituted by its isotope.

The 27th aspect of the present invention is directed to a liquid crystalcomposition which contains at least one of the liquid crystal compoundsdescribed in the 1st aspect to the 22nd aspect of the present inventionas a first component, at least one compound selected from the groupconsisting compounds of the general formulae (5) and (6) as a secondcomponent, and at least one compound selected from the group consistingcompounds of the general formulae (7), (8) and (9) as a third component.

The 28th aspect of the present invention is directed to a liquid crystalcomposition which contains at least one of the liquid crystal compoundsdescribed in the 1st aspect to the 22nd aspect of the present inventionas a first component, at least one compound selected from the groupconsisting compounds of the general formulae (2), (3) and (4) as asecond component, at least one compound selected from the groupconsisting compounds of the general formulae (5) and (6) as a thirdcomponent, and at least one compound selected from the group consistingcompounds of the general formulae (7), (8) and (9) as a fourthcomponent.

The 29th aspect of the present invention is directed to a liquid crystalcomposition which contains a liquid crystal composition described in anyone of the 23rd aspect to the 28th aspect of the present invention andat least one optically active compound.

The 30th aspect of the present invention is directed to a liquid crystaldisplay device constituted by the use of a liquid crystal compositiondescribed in any one of the 23rd aspect to the 29th aspect of thepresent invention.

A novel liquid crystal fluorovinyl derivative compound of the presentinvention has particularly steep threshold properties, a low viscosity,a good compatibility with another liquid crystal compound and a properoptical anisotropy value. Furthermore, a novel liquid crystalcomposition and a liquid crystal display device constituted by usingthis compound have the above excellent characteristics.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described in detail.

In the present invention, R₁ in the general formula (1) is an alkylgroup having 1 to 18 carbon atoms in which a methylene group may besubstituted by an oxygen atom, a sulfur atom, —CH═CH— or —C≡C— and ahydrogen atom may be substituted by a halogen atom or a cyano group.Typical examples of the alkyl group include an alkyl group, alkenylgroup, alkynyl group, alkadienyl group, alkoxy group, alkoxyalkyl group,alkenyloxy group, alkynyloxy group, haloalkyl group and cyanogroup-substituted alkyl group.

More typical examples of the alkyl group include a methyl group, ethylgroup, propyl group, butyl group, pentyl group, vinyl group, 1-propenylgroup, 1-butenyl group, 1-pentenyl group, 3-butenyl group, 3-pentenylgroup, 1-propynyl group, 1-butynyl group, 3-pentynyl group,1,3-butadienyl group, 1,4-pentadienyl group, 1,5-hexadienyl group,1,5-heptadienyl group, methoxy group, ethoxy group, propoxy group,butoxy group, pentoxy group, methoxymethyl group, ethoxymethyl group,propoxymethyl group, butoxymethyl group, methoxyethyl group,propoxymethyl group, methoxypropyl group, ethoxypropyl group, allyloxygroup, 3-butenyloxy group, 2-butynyloxy group, 3-pentynyloxy group,fluoromethyl group, 2-fluoroethyl group, 3-fluoropropyl group,4-fluorobutyl group, 5-fluoropentyl group, 2-fluorobutyl group,2-fluoropentyl group, 2,2-difluorobutyl group, 2,2-difluoropentyl group,3-fluorobutyl group, 3-fluoropentyl group, 3,3-difluorobutyl group,3,3-difluoropentyl group, 4-fluoropentyl group, 4,4-difluoropentylgroup, cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group,4-cyanobutyl group and 5-cyanopentyl group.

In the general formula (1) of the present invention, rings A, B and Care each 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene,1,3-dioxane-2,5-diyl, pyridine-2,5-diyl or pyrimidine-2,5-diyl in whicha hydrogen atom in the ring may be substituted by a halogen atom. In thecase that the low-viscosity liquid crystal is required, the rings A, Band C are each 1,4-cyclohexylene, or 1,4-phenylene or1,3-dioxane-2,5-diyl in which a hydrogen atom in the ring may besubstituted by a halogen atom.

Z₁, Z₂ and Z₃ are each independently a single bond, —CH₂CH₂—, —CH═CH—,—CH₂O—, —OCH₂—, —(CH₂)₄—, —(CH₂)₃—O—, —O—(CH₂)₃—, —(CH₂)₂—CH═CH—,—CH═CH—(CH₂)₂—, —CF₂O—, —OCF₂—, —CR₂═CH—, —CH═CR₂— or —CF═CF—, and R₂ isan alkyl group having 1 to 5 carbon atoms.

In the case that the low-viscosity liquid crystal is required, Z₁, Z₂and Z₃ are each preferably a single bond, —CH₂CH₂—, —CH═CH—,—(CH₂)₂—CH═CH—, —CH═CH—(CH₂)₂—, —CF₂O—, —OCF₂— or —CF═CF—, morepreferably a single bond, —CH═CH—, —CF₂O—, —OCF₂— or —CF═CF—.

In the case that the liquid crystal having a large optical anisotropy isrequired, Z₁, Z₂ and Z₃ are each preferably —CH═CH—, —(CH₂)₂—CH═CH—,—CH═CH—(CH₂)₂—, —CR₂═CH—, —CH═CR₂— or —CF═CF—.

In the formula (1), m is an integer of 0 to 5. In the case that thelow-viscosity liquid crystal is required, m is preferably a small value.Alternatively, in the case that a good liquid crystalline property (awide nematic phase temperature range) and a high elastic constant ratio(K₃₃/K₁₁) are required, m is preferably in the range of 0 to 2.

The compound of the general formula (1) [hereinafter referred to as “thecompound (1)”] has a much higher elastic constant ratio (K₃₃/₁₁) ascompared with conventional compounds, and the liquid crystal compositionusing the compound (1) shows steep threshold properties. Furthermore, inthe compound of the general formula (1), a dependency of the constantratio on a temperature, particularly in a low temperature range, thedependency of the constant ratio on the temperature is far lower than inthe conventional liquid crystal compounds.

The compound (1) has a high compatibility with another liquid crystalcompound or another liquid crystal composition. The liquid crystalcomposition using the compound (1) can keep the nematic phase even at alow temperature (e.g., −20° C. which is practically required).

The compound (1) exhibits a low viscosity, and so when the liquidcrystal composition is prepared by the use of this compound (1), theviscosity of the whole composition does not increase, even if thecontent of the compound (1) is high. Furthermore, the dependency of theviscosity on the temperature, particularly at the low temperature, thedependency of the viscosity on the temperature is extremely low. Whenthis low-viscosity liquid crystal compound is used for the displaydevice, the liquid crystal composition having a high-speed response canbe prepared.

The compound (1) has a suitable optical anisotropy value and a suitabledielectric anisotropy value.

The compound (1) is very chemically stable, and the liquid crystalcomposition in which this compound (1) is used has a very high specificresistance and voltage holding ratio. This compound (1) is alsoremarkably stable to external factors such as ultraviolet light andheat, and hence it shows a chemical stability which is satisfactory as aconstitutional element of the practical liquid crystal composition.

An optional constitutional element of the compound (1) may besubstituted by a corresponding isotope, because even when such asubstitution is made, the characteristics of the compound (1) does notchange.

The compound of the present invention is particularly suitable for thepreparation of the liquid crystal composition for STN, but it can alsobe suitably applied to other uses. For example, this compound can beutilized as a liquid crystal compound for TN, a liquid crystal compoundfor a guest-host mode, a liquid crystal compound for a polymerdispersion type liquid crystal device, a liquid crystal compound for adynamic scattering mode, a liquid crystal compound for an active matrix,a compound for a ferroelectric liquid crystal, a compound for ananti-ferroelectric liquid crystal and the like.

A liquid crystal composition of the present invention contains 0.1 to99.9% by weight, preferably 1 to 50% by weight, more preferably 3 to 20%by weight of one or more of the compounds (1), and this compositionexpresses excellent characteristics.

Another liquid crystal composition which can be provided by the presentinvention contains at least one of the compounds (1) at a firstcomponent and another compound optionally selected from the groupconsisting of compounds represented by the general formulae (2) to (9)in compliance with a purpose of the liquid crystal composition.

Preferable examples of the compounds represented by the general formulae(2) to (4) include the following compounds:

wherein R₃ and Y₁ are as defined above.

The compounds represented by the general formulae (2) to (4) haveposidielectric anisotropy values, and they are essential to prepare theliquid crystal composition for TFT (AM-LCD) in which highly reliablecharacteristics such as an excellent thermal stability and chemicalstability as well as a high voltage holding ratio (or a high specificresistance) are required.

In the case that the liquid crystal composition for TFT is prepared, theamount of any compound of the general formulae (2) to (4) to be used isin the range of 1 to 99% by weight, preferably 10 to 97% by weight, morepreferably 40 to 95% by weight with respect to the total weight of theliquid crystal composition. In preparing the liquid crystal compositionfor TFT, any of the compounds of the general formulae (7) to (9) may beused. Also in preparing the liquid crystal composition for an STNdisplay system or a TN display system, any of the compounds of thegeneral formulae (2) to (4) may be used. In this case, the amount of anycompound of the general formulae (2) to (4) is preferably 50% by weightor less, because the compound has a less effect of decreasing thethreshold voltage of the liquid crystal composition, as compared withthe compounds of the general formulae (5) and (6).

Preferable examples of the compounds represented by the general formulae(5) to (7) include the following compounds:

wherein R₄, R₅ and Y₂ are as defined above.

The compounds represented by the general formulae (5) and (6) havepositive and large dielectric anisotropy values, and they can be usedfor the purpose of decreasing the threshold voltage. Furthermore, theycan also be used for the purpose of the enlargement of a nematic rangesuch as the adjustment of the optical anisotropy value, the rise of aclearing point or the like. Alternatively, they can also be used inorder to improve the steepness of the threshold voltage of the liquidcrystal composition for the STN display system or the TN display system.

The compounds of the general formulae (5) and (6) are essential toprepare the liquid crystal composition for the STN display system or theTN display system.

If the amount of the compound of the general formula (5) or (6) isincreased, the threshold voltage of the liquid crystal compositiondecreases and the viscosity increases. Therefore, it is advantageousthat the largest possible amount of the compound having the formula (5)or (6) is used in the range in which the required viscosity of theliquid crystal composition is met, because such a constitution permitsthe drive of the display device at a low voltage.

In the case that the liquid crystal composition for the STN displaysystem or the TN display system is prepared, the amount of the compoundof the general formula (5) or (6) to be used is in the range of 0.1 to99.0% by weight, preferably 10 to 97% by weight, more preferably 40 to95% by weight with respect to the total weight of the liquid crystalcomposition.

Preferable examples of the compounds represented by the general formulae(7) to (9) include the following compounds:

wherein R₆ and R₇ are as defined above.

The compounds represented by the general formulae (7) to (9) have smallabsolute values of the dielectric anisotropy, and so they are nearlyneutral. The compound of the general formula (7) is mainly used for thepurpose of adjusting the viscosity or the optical anisotropy value.Furthermore, the compounds of the general formulae (8) and (9) are usedfor the purpose of the enlargement of the nematic range such as the riseof the clearing point or the like, or for the purpose of the adjustmentof the optical anisotropy value.

When the amount of any compound of the general formulae (7) to (9) isincreased, the threshold voltage of the liquid crystal compositionincreases and the viscosity decreases. Therefore, it is desirable that alargest amount of the compound is used in the range in which therequired threshold voltage of the liquid crystal composition is met. Inthe case that the liquid crystal composition for TFT is prepared, theamount of the compound of the general formulae (7) to (9) to be used isin the range of 40% by weight or less, preferably 35% by weight or lesswith respect to the total weight of the liquid crystal composition. Inthe case that the liquid crystal composition for the STN display systemor the TN display system is prepared, the amount of the compound to beused is 70% by weight or less, preferably 60% by weight or less.

Furthermore, except an especial case of the liquid crystal compositionfor an OCB (optically compensated birefringence) mode or the like, anoptically active compound may be added to the liquid crystal compositionusually for the purposes of forming a helical structure of the liquidcrystal composition, adjusting a necessary twist angle, and preventingreverse twist. For such purposes, any of the known optically activecompounds may be used, but the following optically active compounds arepreferable:

Usually, any of these optically active compounds is added to the liquidcrystal composition of the present invention to regulate a pitch lengthof the twist. In the cases of the liquid crystal compositions for TFTand TN, the pitch length of the twist is preferably regulated so as tobe in the range of 40 to 200 μm. In the case of the liquid crystalcomposition for STN, the pitch length of the twist is preferablyregulated so as to be in the range of 6 to 20 μm. Moreover, in the caseof a bistable TN mode, the pitch length of the twist is preferablyregulated so as to be in the range of 1.5 to 4 μm. In addition, for thepurpose of regulating the dependency of the pitch length on atemperature, two or more kinds of optically active compounds may beadded.

The liquid crystal composition of the present invention can be preparedin a conventional manner. In general, there can be employed a methodwhich comprises mutually dissolving the above various components at ahigh temperature.

Furthermore, the liquid crystal composition of the present invention canbe used as the liquid crystal composition for a guest-host (GH) mode byadding a dichromatic dye such as a merocyanine dye, a styryl dye, an azodye, an azomethine dye, an azoxy dye, a quinophthalone dye, ananthraquinone dye or a tetrazine dye to the liquid crystal composition.Moreover, the liquid crystal composition of the present invention canalso be used as the liquid crystal composition for NCAP in whichmicrocapsules containing the nematic liquid crystal are used, and as theliquid crystal composition for a polymer dispersion type liquid crystaldisplay device (PDLCD) typified by a polymer network liquid crystaldisplay device (PNLCD) in which a three-dimensional network polymer isformed in the liquid crystal. In addition, the liquid crystalcomposition of the present invention can also be used as the liquidcrystal composition for a double refraction control (ECB) mode and adynamic scattering mode (DS).

The compound represented by the general formula (1) of the presentinvention can be manufactured by using a usual chemical technique of anorganic synthesis. For example, by suitably combining known reactionsdescribed in magazines such as Organic Synthesis, Organic Reactions andShin Zikken Kagaku Koza, the compound represented by the general formula(1) can be synthesized.

A fluorovinyl site and a difluorovinyl site at a terminal can be buildup in accordance with a procedure shown by the following reactionformula. That is to say, a cyclohexanone derivative (T-1) prepared by amethod described in literature is subjected to a Wittig reaction by theuse of a phosphonium salt of chloromethyl methyl ether, and theresulting enol ether is then converted under acidic conditions into analdehyde substance (T-2). This aldehyde substance is reacted with sodiumchlorodifluoroacetate in the presence of triphenylphosphine to obtain adifluorocompound of the compounds (1). Furthermore, thisdifluorocompound is subjected to a reduction reaction to prepare amonofluorocompound of the compounds (1).

The compound of the chemical formula (1) in which m is 1 can be preparedby subjecting the above aldehyde substance (T-2) to the reactions of thefollowing reaction formula (b) in turn.

As shown in the following reaction formula (c), the compound of thechemical formula (1) in which m is 2 can be prepared by reacting theabove derivative (T-1) with3-(1,3-dioxane-2-yl)ethyltriphenylphosphonium bromide, reducing theresulting Wittig adduct (T-4), carrying out a protective group removalreaction to obtain an aldehyde substance (T-5), and then subjecting thisaldehyde substance (T-5) to the above reaction.

The compound of the chemical formula (1) in which m is 3 or more can beprepared by suitably combining some reactions of the above reactionformulae (a) and (b).

Description will be made in more detail by the use of the followingreaction formula (d). A cyclohexanone derivative (T-6) or an aldehydesubstance (T-7) is reacted with a phenyllithium derivative prepared froma phenyl bromide (T-8) and a lithium reagent, and then carrying outdehydration and a hydrogenation reaction to obtain a compound (T-9).Next, this compound (T-9) is reacted with the lithium reagent again andthen a compound (T-10) or (T-11), followed by dehydration andhydrogenation to obtain a cyclohexanone derivative (T-12). Thisderivative (T-12) can be converted into a compound (1-2) by the processof the reaction formulae (a) to (c).

Furthermore, as shown by the following reaction formula (e), phenol oran alcohol derivative (T-13) is reacted with a bromide (T-14) in thepresence of basic conditions to obtain an ether (T-15). Next, this etheris subjected to a protective group removal reaction under acidicconditions to obtain a cyclohexanone derivative (T-16), and for thisderivative (T-16), the above reaction formulae (a) to (c) are conductedto obtain a compound (1-3).

Moreover, as shown by the following reaction formula (f), the samereaction as in the above reaction formula (e) is carried out, using acompound (T-17) as a bromide and a compound (T-18) as an alcohol toprepare a compound of the general formula (1-3) in which a methyleneoxygroup is oppositely oriented as compared with the case of the reactionformula (e).

As shown by the following reaction formula (g), an ethyl bromidederivative (T-20) (a Grignard reagent) prepared from the compound (T-17)by a usual carbon homologation reaction is reacted with the compound(T-10), followed by dehydration and reduction, to obtain a cyclohexanonederivative (T-21). The thus obtained (T-21) can be converted by theprocess of the above reaction formulae (a) to (c) into a compound (1-3)in which a bond group is a 1,2-ethylene group.

As shown by the following reaction formula (h), the compound (T-20) isfurther subjected to the carbon homologation reaction to obtain a butylbromide derivative (T-21), and the same reaction as in the abovereaction formula (g) is then conducted to prepare a composition (1-3) inwhich a bond group is a 1,4-butylene group.

As shown by the following reaction formula (i), a phenol derivative(T-22) is reacted with a bromide (T-23) to obtain an ether (T-24). Next,this ether (T-24) is subjected to the process of the above chemicalformula (e) to prepare a compound (1-3) in which Z₂ is OCH₂.

Furthermore, as shown in the following reaction formula (j), a bromide(T-25) is reacted with phenol or an alcohol (T-26) in accordance withthe process of the above (e) to prepare a compound (1-3) in which Z₂ isCH₂O.

As shown in the following reaction formula (k), a phenethyl bromidederivative (T-28) (a Grignard reagent) is reacted with a monoketal(T-29), followed by dehydration, to obtain a cyclohexene derivative(T-30). Next, a cyclohexene ring portion of this derivative (T-30) ishydrogenated, and the resulting cyclohexanone (T-31) is then subjectedto the reactions of the above reaction formulae (a) to (c), therebyobtaining a compound (1-3) in which a ring C is 1,4-cyclohexylene.Moreover, the derivative (T-30) is dehydrogenated with chloranil or thelike to obtain a compound (T-32), and the reactions of the abovereaction formulae (a) to (c) are then conducted to obtain a compound(1-3) in which the ring C is 1,4-phenylene.

As shown in the following reaction formula (l), phenethyl bromide (T-28)is subjected to the carbon homologation reaction to obtain butyl bromide(T-33). Next, butyl bromide (T-33) is subjected to the above reaction(g) to prepare a compound (1-3) in which Z₂ is 1,4-butylene.

As shown in the following reaction formula (m), an aldehyde (T-35)obtained by demethylation and then oxidation of a compound (T-34)described in Japanese Patent Publication No. 16331/1991 is subjected tothe above reactions (a) to (b), thereby obtaining a compound (1-1-1) inwhich m is 0. Alternatively, when the above reactions (a) to (c) areapplied to an aldehyde (T-36) obtained by subjecting the aldehyde (T-35)to the carbon homologation reaction, a compound (1-1-1) in which m is 1or more is obtained.

As shown in the following reaction formula (n), a bromide (T-37) isreacted with the compound (T-10), followed by dehydration and thenhydrogenation, to obtain a cyclohexane derivative (T-38). Thisderivative (T-38) can be converted into a compound (T-39) by the carbonhomologation reaction. The compounds (T-38) and (T-39) can each beconverted into a compound (1-1-2) by the above reactions (a) to (c).

As shown in the following reaction formula (o), a bromide (T-40) isreacted with the compound (T-29), followed by dehydration and thenhydrogenation, to obtain a cyclohexanone derivative (T-41). Thisderivative (T-41) can be converted into a compound (T-42) by the carbonhomologation reaction. The compounds (T-41) and (T-42) can each beconverted into a compound (1-1-3) by the above reactions (a) to (c).

As shown in the following reaction formula (p), a cis-olefin (T-45)obtained from a phosphonium salt (T-43) and an aldehyde (T-44) issubjected to inversion of a conformation to obtain a compound (T-46).The inversion reaction can be suitably carried out in a manner describedin Japanese Patent Publication Nos. 2653/1995 and 2654/1995. Thiscompound (T-46) is reduced with DIBAL (diisobutylaluminum hydride) toobtain an aldehyde (T-47). This aldehyde (T-47) can be converted into acompound (T-48) by the usual carbon homologation reaction. The compounds(T-47) and (T-48) can each be converted into a compound (1-4-1) by theabove reactions (a) to (c).

As shown in the following reaction formula (q), compounds (1-4-2) and(1-4-3) can be prepared from compounds (T-49) and (T-50), respectively,in accordance with the procedure (p).

As shown in the following reaction formula (r), an iodide (T-51) isreacted with butyl lithium and tetrafluoroethylene in turn to obtain acompound (T-52). A compound (T-53) similarly treated with the base isthen reacted with the above compound (T-52) to obtain a compound (T-54).Afterward, this compound (T-54) is substituted jected to the reactions(a) to (c), thereby preparing a compound (1-4-4).

As shown in the following reaction formula (s), a dithiocarboxylic acid(T-55) prepared from a Grignard reagent of a phenyl halide and carbondisulfide is converted into an acid chloride. Next, this compound isreacted with a phenol (T-56) to obtain a thioester, and this thioesteris then fluorinated with DAST (diethylaminosulfur trifluoride) to obtaina compound (T-57). Afterward, this compound (T-57) is subjected to thereactions (a) to (c), thereby preparing a compound (1-4-5).

As shown in the following reaction formula (t), a compound (1-4-5) canbe prepared in accordance with the above process (s) by the use of aphenol (T-58) and a dithiocarboxylic acid (T-59).

As shown in the following reaction formula (u), a compound (1-4-6) canbe prepared by subjecting a cyclohexanone (T-62) obtained from a ketone(T-60) and a bromide (T-61) to the above reactions (a) to (c).

As shown in the following reaction formula (v), a compound (1-4-7) canbe prepared by subjecting a cyclohexanone (T-65) obtained from a ketone(T-63) and a bromide (Y-64) to the above reactions (a) to (c).

EXAMPLES

Next, the present invention will be described in more detail withreference to examples. The scope of the present invention should not belimited to these examples at all.

Example 1

Preparation of4′-propyl-4-(4-(4-(4-fluoro-3-butenyl)cyclohexyl)cyclohexyl)biphenyl [acompound of the general formula (1) in which R₁=a propyl group, a ringA=a ring B=1,4-phenylene, a ring C=1,4-cyclohexylene, Z₁=Z₂=Z₃=a singlebond, p=q=1, m=2, and X=a hydrogen atom]

To a mixture of 2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium bromide(110 mmol) and 50 ml of THF, t-BuOK (110 mmol) was added, followed bystirring at room temperature for 30 minutes. Next, 50 ml of a THFsolution containing4-(4-(4′-propylbiphenyl-4-yl)cyclohexyl)cyclohexanone (100 mmol)prepared from 4′-propyl-4-bromobiphenyl andbicyclohexandione=monoethylene ketal in accordance with a process ofJapanese Patent Application Laid-open No. 211711/1994 was added theretoat 0° C. or less, followed by stirring at the same temperature for 2hours.

THF was removed under reduced pressure, and 500 ml of heptane was thenadded thereto. Next, the precipitated crystals were removed byfiltration, and the resulting filtrate was then concentrated. To theresidue, there were added 30 ml of toluene, 100 ml of ethanol and 10 gof 5% palladium carbon, and the mixture was then stirred under ahydrogen atmosphere for 14 hours. After it was confirmed that theabsorption of the hydrogen gas stopped, the catalyst was removed byfiltration. The filtrate was concentrated, and the residue wasrecrystallized from ethanol 3 times, thereby obtaining4′-propyl-4-(4-(4-(2-(1,3-dioxane-2-yl)ethyl)cyclohexyl)cyclohexyl)biphenyl(33 mmol).

A mixture of4′-propyl-4-(4-(4-(2-(1,3-dioxane-2-yl)ethyl)cyclohexyl)cyclohexyl)biphenyl(30 mmol), 100 ml of toluene and 30 ml of formic acid was refluxed for 2hours, and the reaction product was then cooled to room temperature.Afterward, the reaction product was sufficiently washed with water,saturated sodium hydrogencarbonate and water in this order, and thendried over anhydrous magnesium sulfate. The solvent was removed underreduced pressure, and the resulting residue was then recrystallized fromheptane, thereby obtaining3-(4-(4-(4′-propylbiphenyl-4-yl)cyclohexyl)cyclohexyl)propanal (25mmol).

To a mixture of3-(4-(4-(4′-propylbiphenyl-4-yl)cyclohexyl)cyclohexyl)propanal (25mmol), triphenylphosphine (26 mmol) and 70 ml of dry DMF, 60 ml of a DMFsolution containing sodium chlorodifluoroacetate (26 mmol) was addeddropwise at about 100° C. After the completion of the dropping, thesolution was stirred for 30 minutes, while the same temperature wasmaintained. After the solution was cooled to room temperature, 100 ml oftoluene was added, followed by extraction.

The solvent was removed, and the resulting residue was purified bycolumn chromatography (a toluene-heptane mixing solvent) and thenrecrystallization (heptane) to obtain4′-propyl-4-(4-(4-(4,4-difluoro-3-butenyl)cyclohexyl)cyclohexyl)biphenyl(19 mmol) [a compound of the general formula (1) in which R₁=a propylgroup, a ring A=a ring B=1,4-phenylene, a ring C=1,4-cyclohexylene,Z₁=Z₂=Z₃=a single bond, p=q=0, m=2, and X=a fluorine atom].

Solution of sodium bis(2-methoxyethoxy)aluminum hydride in toluene(Red-Al 17 mmol) was added to a mixture of4′-propyl-4-(4-(4-(4,4-difluoro-3-butenyl)cyclohexyl)cyclohexyl)biphenyl(15 mmol) and 50 ml of THF, followed by reflux for 10 hours. Next, thereaction product was poured into 200 ml of 2M hydrochloric acid, andextraction was then carried out with 100 ml of toluene. After theresulting organic layer was separated and then dried, the solvent wasremoved, and the residue was purified by column chromatography (atoluene-heptane mixing solvent) and next recrystallization (heptane) toobtain the desired compound (4 mmol). Its structure was properlysupported by spectrum data.

In accordance with the procedure of Example 1, the compounds representedby the following formula (1-1-3) were prepared.

Typically, the compounds shown in Tables 1 and 2 were prepared.

TABLE 1 r R₁ L1 L2 L3 L4 L5 L6 L7 L8 m X 0 C₃H₇ H H H H H H H H 0 H 0C₃H₇ H H H H H H H H 0 F 0 CH₂═CH H H H H H H H H 0 F 0 C₅H₁₁ H H H H HH H H 0 F 0 C₃H₇ H F H H H H H H 0 F 0 C₃H₇ H H H H H F H H 0 F 0 C₃H₇ HF H H H F H H 0 F 0 CH₃O F H H H H H H H 0 F 0 C₃H₇ H H H H H H H H 1 H0 C₃H₇ H H H H H H H H 1 F 0 C₃H₇ H H H H H H H H 2 F 0 C₃H₇ H F H H H HH H 2 F 0 C₅H₁₁ F F H H H H H H 2 F 0 C₃H₇ H H H H H H H H 3 F 0 C₅H₁₁ HH H H H H H H 4 F 0 C₃H₇ H H H H H H H H 5 H

TABLE 2 r R₁ L1 L2 L3 L4 L5 L6 L7 L8 m X 1 C₃H₇ H H H H H H H H 0 H 1C₃H₇ H H H H H H H H 0 F 1 CH₂═CH H H H H H H H H 0 F 1 C₅H₁₁ H H H H HH H H 0 F 1 C₃H₇ H F H H H H H H 0 F 1 C₃H₇ H H H H H F H H 0 F 1 C₃H₇ HF H H H F H H 0 F 1 CH₃O F H H H H H H H 0 F 1 C₃H₇ H H H H H H H H 1 H1 C₃H₇ H H H H H H H H 1 F 1 C₃H₇ H H H H H H H H 2 F 1 C₃H₇ H F H H H HH H 2 F 1 C₅H₁₁ F F H H H H H H 2 F 1 C₃H₇ H H H H H H H H 3 F 1 C₅H₁₁ HH H H H H H H 4 F 1 C₃H₇ H H H H H H H H 5 H

In accordance with the procedure of Example 1, the compounds representedby the following formula (1-1-1) were prepared.

Typically, the compounds shown in Table 3 were prepared. In thefollowing tables, transition temperatures (° C.) of compounds are added,and C, S, N and I mean a crystalline phase, a smectic phase, a nematicphase and an isotropic phase, respectively.

TABLE 3 R₁ L1 L2 L3 L4 L5 L6 L7 L8 m X C₃H₇ H H H H H H H H 0 H C₃H₇ H HH H H H H H 0 F C₄H₉ H H H H H H H H 0 H C₅H₁₁ H H H H H H H H 0 F*1)CH₂═CH H H H H H H H H 0 F

H H H H H H H H 0 F

H H H H H H H H 0 F

H H H H H H H H 0 F C₃H₇ H F H H H H H H 0 F C₃H₇ H H H H F H H H 0 FC₃H₇ F F H H H H H H 0 F C₃H₇ H H H H H H H H 2 H C₃H₇ H H H H H H H H 2F C₃H₇ H F H H H H H H 2 F C₅H₁₁ H H H H F H H H 2 F *1)C 56.8 S 214.3 N268.3 I

In accordance with the procedure of Example 1, the compounds representedby the following formula (1-1-2) were prepared.

Typically, the compounds shown in Tables 4 and 5 were prepared.

TABLE 4 r R₁ L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 L11 L12 m X 0 C₃H₇ H H H H HH H H H H H H 0 H 0 C₃H₇ H H H H H H H H H H H H 0 F 0 C₃H₇ H H H H H FH H H H H H 0 F 0 C₅H₁₁ H H H H H F H H H H H H 0 F 0 CH₃OCH₂ H H H H HF F H H H H H 0 F 0 C₃H₇ H H H H F H H F H H H H 0 F 0 C₃H₇ H H H H H HH H H H H H 2 F 0 C₅H₁₁ H H H H H H H H H H H H 2 F 0 C₃H₇ H H H H H H HH H H H H 4 F

TABLE 5 r R₁ L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 L11 L12 m X 1 C₃H₇ H H H H HH H H H H H H 0 H 1 C₃H₇ H H H H H H H H H H H H 0 F 1 C₃H₇ H H H H H FH H H H H H 0 F 1 C₅H₁₁ H H H H H F H H H H H H 0 F 1 CH₃OCH₂ H H H H HF F H H H H H 0 F 1 C₃H₇ H H H H F H H F H H H H 0 F 1 C₃H₇ H H H H H HH H H H H H 2 F 1 C₅H₁₁ H H H H H H H H H H H H 2 F 1 C₃H₇ H H H H H H HH H H H H 4 F

In accordance with the procedure of Example 1, the compounds representedby the following formula (1-1) were prepared.

Typically, the compounds shown in Table 6 were prepared.

TABLE 6 R₁

m X C₃H₇

0 H C₃H₇

0 F C₃H₇

0 F C₃H₇

2 F C₃H₇

0 F C₃H₇

2 F C₃H₇

0 F C₃H₇

0 H C₃H₇

0 F C₃H₇

2 F C₃H₇

4 F C₃H₇

0 F

Example 2

Preparation of2,3-difluoro-4-(4-propylcyclohexyl)-1-(4-(2,2-difluoroethenyl)cyclohexyl)benzene[a compound of the general formula (1) in which R₁=a propyl group, aring C=2,3-difluoro-1,4-phenylene, a ring B=1,4-cyclohexylene, Z₂=Z₃=asingle bond, p=0, q=1, m=0, and X=a fluorine atom]

A hexane solution (corresponding to 49 mmol) sec-butyl lithium was addeddropwise at −78° C. to 90 ml of a THF solution containing2,3-difluoro-1-(4-propylcyclohexyl)benzene (45 mmol) prepared from2,3-difluorobromobenzene and 4-propylcyclohexanone in accordance with aprocess of Japanese Patent Application Laid-open No. 176240/1984,followed by stirring for 30 minutes.

Next, 50 ml of a THF solution containing cyclohexane-1,4-dione=monoketal(49 mmol) was added to the solution at the same temperature, and thetemperature of the mixture was gradually raised to room temperature.Afterward, 90 ml of water was added, and the solution was thensufficiently extracted with ethyl acetate. The resulting organic layerwas dried over anhydrous magnesium sulfate. The solvent was removedunder reduced pressure, and to the residue, 100 ml of toluene andp-toluene-sulfonic acid monohydrate (2 mmol) were added. The solutionwas then refluxed for 5 hours, while water produced was removed.

After cooling, the solution was sufficiently washed with water, and thendried over anhydrous magnesium sulfate. The solvent was removed underreduced pressure, and the residue was purified by column chromatography(toluene) to obtain4-(2,3-difluoro-4-(4-propylcyclohexyl)phenyl)cyclohex-3-enone (29 mmol).To the thus obtained product, 50 ml of ethanol and 1 g of Raney nickelwere added, followed by stirring under a hydrogen atmosphere for 5hours.

After it was confirmed that the absorption of the hydrogen gas stopped,the catalyst was removed by filtration. The filtrate was concentrated toobtain 4-(2,3-difluoro-4-(4-propylcyclohexyl)phenyl)cyclohexanone (25mmol). This product was a mixture of a cis form and a trans form, but itwas used in the next reaction as it was.

A mixture of methoxymethyltriphenylphosphonium chloride (27 mmol),t-BuOK (28 mmol) and 50 ml of THF was stirred at room temperature for 1hour to obtain a red solution. Next, 80 ml of a THF solution containing4-(2,3-difluoro-4-(4-propylcyclohexyl)phenyl)cyclohexanone (25 mmol) wasadded at SoC or less, followed by stirring for 2 hours. The solvent wasremoved under reduced pressure, and 200 ml of heptane was added to theresidue. Afterward, the precipitated crystals were removed byfiltration, and the resulting filtrate was then concentrated to obtainan enol ether.

Furthermore, a mixture of the enol ether (25 mmol), 60 ml of THF and 60ml of 6M hydrochloric acid was stirred at room temperature overnight.The solution was extracted with 100 ml of toluene, and the solvent wasremoved under reduced pressure. The resulting residue was purifiedthrough column chromatography (toluene) to obtain4-(2,3-difluoro-4-(4-propylcyclohexyl)phenyl)cyclohexanecarboaldehyde(19 mmol).

To a mixture of4-(2,3-difluoro-4-(4-propylcyclohexyl)phenyl)cyclohexanecarboaldehyde(19 mmol), triphenylphosphine (22 mmol) and 70 ml of dry DMF, 60 ml of aDMF solution containing sodium chlorodifluoroacetate (23 mmol) was addeddropwise at about 100° C. After the completion of the dropping, thesolution was stirred for 30 minutes, while the same temperature wasmaintained. After the solution was cooled to room temperature, 100 ml oftoluene was added, followed by extraction. The solvent was removed, andthe resulting residue was purified by repeating column chromatography (atoluene-heptane mixing solvent) and then recrystallization (heptane) toobtain the desired compound (3.5 mmol). Its structure was properlysupported by spectrum data.

In accordance with the procedure of Example 2, the compounds representedby the following formula (1-2) were prepared.

Typically, the compounds shown in Tables 7 to 10 were prepared.

TABLE 7 r s R₁ L1 L2 L3 L4 m X 0 0 C₃H₇ H H H H 0 H 0 0 C₅H₁₁ H H H H 0H 0 0 C₃H₇ H H H H 0 F 0 0 C₅H₁₁ H H H H 0 F 0 0 CH₂═CH H H H H 0 F 0 0C₃H₇ F H H H 0 F 0 0 C₃H₇ H F H H 0 F 0 0 C₃H₇ F F H H 0 F 0 0 C₅H₁₁ F FH H 0 F *2) 0 0 C₃H₇ F F F H 0 F 0 0 C₃H₇ H H H H 2 F 0 0 C₃H₇ F H H H 2F 0 0 C₃H₇ H F H H 2 F 0 0 C₃H₇ F F H H 2 F 0 0 C₃H₇ H H H H 4 F *2) C95.3 N 113.2 I

TABLE 8 r s R₁ L1 L2 L3 L4 m X 1 0 C₃H₇ H H H H 0 H 1 0 C₅H₁₁ H H H H 0H 1 0 C₃H₇ H H H H 0 F *3) 1 0 C₅H₁₁ H H H H 0 F 1 0 CH₂═CH H H H H 0 F1 0 C₃H₇ F H H H 0 F 1 0 C₃H₇ H F H H 0 F 1 0 C₃H₇ F F H H 0 F 1 0 C₅H₁₁F F H H 0 F 1 0 C₃H₇ F F F H 0 F 1 0 C₃H₇ H H H H 2 F 1 0 C₃H₇ F H H H 2F 1 0 C₃H₇ H F H H 2 F 1 0 C₃H₇ F F H H 2 F 1 0 C₃H₇ H H H H 4 F *3) C54.2 S 80.4 N 120.3 I

TABLE 9 r s R₁ L1 L2 L3 L4 m X 0 1 C₃H₇ H H H H 0 H 0 1 C₅H₁₁ H H H H 0H 0 1 C₃H₇ H H H H 0 F 0 1 C₅H₁₁ H H H H 0 F 0 1 CH₂═CH H H H H 0 F 0 1C₃H₇ F H H H 0 F 0 1 C₃H₇ H F H H 0 F 0 1 C₃H₇ F F H H 0 F 0 1 C₅H₁₁ F FH H 0 F 0 1 C₃H₇ F F F H 0 F 0 1 C₃H₇ H H H H 2 F 0 1 C₃H₇ F H H H 2 F 01 C₃H₇ H F H H 2 F 0 1 C₃H₇ F F H H 2 F 0 1 C₃H₇ H H H H 4 F

TABLE 10 r s R₁ L1 L2 L3 L4 m X 1 1 C₃H₇ H H H H 0 H 1 1 C₅H₁₁ H H H H 0H 1 1 C₃H₇ H H H H 0 F 1 1 C₅H₁₁ H H H H 0 F 1 1 CH₂═CH H H H H 0 F 1 1C₃H₇ F H H H 0 F 1 1 C₃H₇ H F H H 0 F 1 1 C₃H₇ F F H H 0 F 1 1 C₅H₁₁ F FH H 0 F 1 1 C₃H₇ F F F H 0 F 1 1 C₃H₇ H H H H 2 F 1 1 C₃H₇ F H H H 2 F 11 C₃H₇ H F H H 2 F 1 1 C₃H₇ F F H H 2 F 1 1 C₃H₇ H H H H 4 F

Example 3

Preparation of4-(4-(4-(4-pentylphenyl)butyl)yclohexyl)-1-(2,2-difluoroethenyl)cyclohexane[a compound of the general formula (1) in which R₁=a pentyl group, aring B=1,4-phenylene, a ring C=1,4-cyclohexylene, Z₂=1,4-butylene, Z₃=asingle bond, p=0, q=1, m=0, and X=a fluorine atom]

A mixture of methoxymethyltriphenylphosphonium chloride (55 mmol),t-BuOK (58 mmol) and 100 ml of THF was stirred at room temperature for 1hour to obtain a red solution. Next, 100 ml of a THF solution containing4-(4-(4-(4-pentylphenyl)butyl)cyclohexyl)cyclohexanone (50 mmol)prepared from 4-(4-pentylphenyl)butyl bromide andbicyclohexanedione=monoethylene ketal in accordance with a process ofJapanese Patent Application Laid-open No. 211711/1994 was added at 5° C.or less, followed by stirring for 2 hours. The solvent was removed underreduced pressure, and 400 ml of heptane was added to the residue.Afterward, the precipitated crystals were removed by filtration, and theresulting filtrate was then concentrated to obtain an enol ether.

Furthermore, a mixture of the enol ether, 100 ml of THF and 120 ml of 6Mhydrochloric acid was stirred at room temperature overnight. Thesolution was extracted with 100 ml of toluene, and the solvent wasremoved under reduced pressure. The resulting residue was purifiedthrough column chromatography (toluene) to obtain4-(4-(4-(4-pentylphenyl)butyl)cyclohexyl)cyclohexanecarboaldehyde (42mmol).

To a mixture of4-(4-(4-(4-pentylphenyl)butyl)cyclohexyl)cyclohexanecarboaldehyde (42mmol), triphenylphosphine (45 mmol) and 140 ml of dry DMF, 150 ml of aDMF solution containing sodium chlorodifluoroacetate (47 mmol) was addeddropwise at about 100° C. After the completion of the dropping, thesolution was stirred for 30 minutes, while the same temperature wasmaintained. After the solution was cooled to room temperature, 200 ml oftoluene was added, followed by extraction. The solvent was removed, andthe resulting residue was purified by column chromatography (atoluene-heptane mixing solvent) and then recrystallization(ethanol-benzene) to obtain the desired compound (21 mmol). Itsstructure was properly supported by spectrum data.

In accordance with the procedure of Example 3, the compounds representedby the following formula (1-3) were prepared.

Typically, the compounds shown in Tables 11 to 14 were prepared.

TABLE 11 Z2 Z3′

R₁ L1 L2 L3 L4 m X — CH₂CH₂

C₃H₇ H H H H 0 F — CH₂CH₂

C₃H₇ H H H H 0 F — CH₂CH₂

C₃H₇ F H H H 0 F — CH₂CH₂

C₃H₇ F F H H 0 F — CH₂CH₂

H H H H 2 F — CH₂CH₂

C₃H₇ H H H H 0 F — CH₂CH₂

C₃H₇ H F H H 2 F — CH₂O

C₃H₇ H H H H 0 F — CH₂O

C₅H₁₁ H H H H 0 F — OCH₂

C₃H₇ H H H H 0 F — OCH₂

C₃H₇ F H H H 0 F — OCH₂

C₃H₇ H H H H 0 F

TABLE 12 Z2 Z3

R₁ L1 L2 L3 L4 m X (CH₂)₄ —

C₃H₇ H H H H 0 F (CH₂)₄ —

C₃H₇ H H H H 0 F (CH₂)₄ —

C₃H₇ F H H H 0 F (CH₂)₄ —

C₃H₇ F F H H 0 F (CH₂)₄ —

C₃H₇ H H H H 2 F (CH₂)₄ —

C₃H₇ H H H H 0 F (CH₂)₄ —

C₃H₇ H F H H 2 F

TABLE 13 Z2 Z3

R₁ L1 L2 L3 L4 m X — CH₂CH₂

C₃H₇ H H H H 0 H — CH₂CH₂

C₃H₇ H H H H 0 F — CH₂CH₂

C₃H₇ F H H H 0 F — CH₂CH₂

CH₃O H H H H 0 F — CH₂CH₂

C₃H₇ H H H H 2 F — CH₂CH₂

C₃H₇ H H H H 0 F — CH₂CH₂

C₃H₇ F H H H 0 F — CH₂CH₂

C₃H₇ F H H F 0 F — CH₂CH₂

C₃H₇ H H H H 0 F — CH₂CH₂

C₃H₇ H F H H 0 F — CH₂CH₂

C₃H₇ H F H H 0 F — CH₂CH₂

C₃H₇ H H H H 2 F — CH₂O

C₃H₇ H H H H 0 F — CH₂O

C₃H₇ H H H H 0 F — OCH₂

C₃H₇ F H H H 4 F

TABLE 14 Z2 Z3

R₁ L1 L2 L3 L4 m X — (CH₂)₄

C₃H₇ H H H H 0 H — (CH₂)₄

C₃H₇ H H H H 0 F — (CH₂)₄

C₃H₇ F H H H 0 F — (CH₂)₄

CH₃O H H H H 0 F — (CH₂)₄

C₃H₇ H H H H 2 F — (CH₂)₄

C₃H₇ H H H H 0 F — (CH₂)₄

C₃H₇ F H H H 0 F — (CH₂)₄

C₃H₇ F H H F 0 F — (CH₂)₄

C₃H₇ H H H H 0 F — (CH₂)₄

C₃H₇ H F H H 0 F — (CH₂)₄

C₃H₇ H F H H 0 F — (CH₂)₄

C₃H₇ H H H H 2 F

Example 4

Preparation of4-(2-(4-propylcyclohexyl)ethenyl)-1-(2,2-difluoroethenyl)cyclohexane [acompound of the general formula (1) in which R₁=a propyl group, a ringC=1,4-cyclohexylene, Z₃=—CH═CH—, p=q=0, m=0, and X=a fluorine atom]

A mixture of ethyl4-(2-(4-propylcyclohexyl)ethenyl)cyclohexanecarboxylate (20 mmol) and 50ml of toluene was cooled to −60° C. or less, and a toluene solution(corresponding to 22 mol) of diisobutylaluminum hydride was then addeddropwise, followed by gradually raising the temperature of the solutionto room temperature.

The reaction product was poured into a 3M hydrochloric acid, and 50 mlof toluene was added, followed by extraction. The resulting organiclayer was sufficiently washed, and then dried over anhydrous magnesiumsulfate. The solvent was removed under reduced pressure, and the residuewas purified through column chromatography (toluene) to obtain4-(2-(4-propylcyclohexyl)ethenyl)cyclohexanecarboaldehyde (13 mmol).

To a mixture of4-(2-(4-propylcyclohexyl)ethenyl)cyclohexanecarboaldehyde (13 mmol),triphenylphosphine (15 mmol) and 60 ml of dry DMF, 50 ml of a DMFsolution containing sodium chlorodifluoroacetate (18 mmol) was addeddropwise at about 100° C. After the completion of the dropping, thesolution was stirred for 30 minutes, while the same temperature wasmaintained. After the solution was cooled to room temperature, 100 ml oftoluene was added, followed by extraction. The solvent was removed, andthe resulting residue was purified by column chromatography (atoluene-heptane mixing solvent) and then recrystallization(ethanol-benzene) to obtain the desired compound (11 mmol). Itsstructure was properly supported by spectrum data.

In accordance with the procedure of Example 4, the compounds representedby the following formula (1-4-1) were prepared.

Typically, the compounds shown in Table 15 were prepared.

TABLE 15

R₁ m X

CH₃ 0 H

C₃H₇ 0 H

C₂H₅ 0 F

C₅H₁₁ 0 F

1 F

C₃H₇ 2 F

C₅H₁₁ 2 F

C₃H₇ 4 F

C₃H₇ 0 F

C₃H₇ 0 F

In accordance with the procedure of Example 4, the compounds representedby the following formula (1-4-2) were prepared.

Typically, the compounds shown in Table 16 were prepared.

TABLE 16

R₁ m X

C₂H₅ 0 H

C₃H₇ 0 H

C₂H₅ 0 F

C₃H₇ 0 F

C₅H₁₁ 0 F

C₂H₅ 2 H

2 H

C₂H₅ 2 F

C₃H₇ 2 F

C₅H₁₁ 2 F

C₃H₇ 4 F

C₂H₃ 0 H

C₃H₇ 0 H

C₂H₅ 0 F

C₃H₇ 0 F

C₅H₁₁ 0 F

C₂H₅ 2 F

C₃H₇ 2 F

C₂H₅ 4 F

C₃H₇ 0 F

C₃H₇ 2 F

In accordance with the procedure of Example 4, the compounds representedby the following formula (1-4-3) were prepared.

Typically, the compounds shown in Table 17 were prepared.

TABLE 17

R₁ m X

C₂H₅ 0 H

C₃H₇ 0 H

C₂H₅ 0 F

0 F

C₅H₁₁ 0 F

C₂H₅ 2 F

C₃H₇ 2 H

C₂H₅ 2 H

C₃H₇ 2 F

C₅H₁₁ 2 F

C₃H₇ 4 F

C₂H₃ 0 H

C₃H₇ 0 H

C₂H₅ 0 F

C₃H₇ 0 F

C₅H₁₁ 0 F

C₂H₅ 2 F

C₃H₇ 2 F

C₂H₅ 4 F

C₃H₇ 0 F

C₃H₇ 2 F

Example 5

Preparation of4-(4-(1,2-difluoro-2-(4-propylphenyl)ethenyl)phenyl)-1-(2,2-difluoroethenyl)cyclohexane[a compound of the general formula (1) in which R₁=a propyl group, aring B=a ring C=1,4-phenylene, Z₂=—CF═CF—, Z₃=a single bond, p=0, q=1,m=0, and X=a fluorine atom]

A hexane solution (corresponding to 27 mmol) of butyl lithium was addedat −78° C. to 95 ml of a THF solution containing4-(4-(1,3-dioxane-2-yl)cyclohexyl)phenyl iodide (30 mmol), followed bystirring at the same temperature for 30 minutes. Next,tetrafluoroethylene (corresponding to 33 mmol) was added thereto througha bubbling tube, and the solution was then stirred at the sametemperature for 1 hour.

A hexane solution (corresponding to 27 mmol) of butyl lithium was addedat −78° C. to 95 ml of a THF solution of 4-propylphenyl iodide (30mmol), followed by stirring at the same temperature for 30 minutes. Thissolution was gradually added dropwise to the above solution, and thetemperature of the solution was then raised to room temperature. Next,50 ml of methanol and 50 ml of water were slowly added in this order,and the solvent was removed under reduced pressure. The resultingresidue was purified through column chromatography (toluene) to obtain2-(4-(4-(1,2-difluoro-2-(4-propylphenyl)ethenyl)phenyl)cyclohexyl)-1,3-dioxane(12 mmol).

A mixture of2-(4-(4-(1,2-difluoro-2-(4-propylphenyl)ethenyl)phenyl)cyclohexyl)-1,3-dioxane(12 mmol), 40 ml of toluene and 20 ml of formic acid was stirred at 50°C. for 1 hour. Afterward, the temperature of the solution was raised toroom temperature, and solution was sufficiently washed with water, andthen dried over anhydrous magnesium sulfate. The solvent was removedunder reduced pressure, and the residue was purified through columnchromatography (toluene) to obtain4-(4-(1,2-difluoro-2-(4-propylphenyl)ethenyl)phenyl)cyclohexanecaboaldehyde(8 mmol).

To a mixture of4-(4-(1,2-difluoro-2-(4-propylphenyl)ethenyl)phenyl)cyclohexanecaboaldehyde(8 mmol), triphenylphosphine (9 mmol) and 40 ml of dry DMF, 30 ml of aDMF solution containing sodium chlorodifluoroacetate (9 mmol) was addeddropwise at about 80° C. After the completion of the dropping, thesolution was cooled to room temperature, 50 ml of toluene was added,followed by extraction. The solvent was removed, and the resultingresidue was purified by column chromatography (a toluene-heptane mixingsolvent) and then recrystallization (ethanol-benzene) to obtain thedesired compound (2 mmol). Its structure was properly supported byspectrum data.

In accordance with the procedure of Example 5, the compounds representedby the following formula (1-4-4) were prepared.

Typically, the compounds shown in Tables 18 and 19 were prepared.

TABLE 18 R₁ m X CH₃ 0 H C₂H₅ 0 H C₃H₇ 0 H C₄H₉ 0 H C₅H₁₁ 0 H CH₃ 0 FC₂H₅ 0 F C₃H₇ 0 F C₄H₉ 0 F C₅H₁₁ 0 F C₄H₉ 1 F C₃H₇ 2 F C₂H₅ 3 F C₃H₇ 4 Fp = 0

TABLE 19

R₁ m X

C₃H₇ 0 F

C₃H₇ 2 F

C₃H₇ 0 F

C₃H₇ 0 F

C₃H₇ 0 F

C₃H₇ 0 H

C₃H₇ 0 F

C₃H₇ 0 F

C₂H₅ 0 F

C₂H₅ 0 F p = 1

Example 6

Preparation of4-(4-(4-propylphenyldifluoromethoxy)phenyl)-1-(2,2-difluoroethenyl)cyclohexane[a compound of the general formula (1) in which R₁=a propyl group, aring B=a ring C=1,4-phenylene, Z₂=—CF₂O—, Z₃=a single bond, p=0, q=1,m=0, and X=a fluorine atom]

A mixture of 4-propylphenyldithiocarboxylic acid (50 mmol), thionylchloride (55 mmol) and 100 ml of toluene was stirred at 50° C. for 1hour. Afterward, excessive thionyl chloride was removed under reducedpressure to obtain an acid chloride as a residue. Next, this acidchloride was added to a mixture of4-(4-(1,3-dioxane-2-yl)cyclohexyl)phenol (60 mmol) and 100 ml ofpyridine, and the solution was then stirred at 45° C. for 5 hours. Thetemperature of the solution was returned to room temperature, andextraction was then carried out with 50 ml of toluene. The resultingorganic layer was sufficiently washed with water, and then dried overanhydrous magnesium sulfate. The solvent was removed under reducedpressure, and the residue was purified through column chromatography(toluene-heptane) to obtain a thione ester (23 mmol).

Diethylaminosulfur trifluoride (25 mmol) was added to 30 ml of amethylene chloride solution containing the thione ester (20 mmol),followed by stirring at room temperature for 2 hours. Afterward, 50 mlof water and 30 ml of toluene were added, and the solution was stirredand the separated organic layer was then concentrated under reducedpressure. The residue was recrystallized from ether to obtain2-(4-(4-(4-propylphenyl)difluoromethoxy)phenyl)cyclohexyl-1,3-dioxane(12 mmol).

A mixture of2-(4-(4-(4-propylphenyl)difluoromethoxy)phenyl)cyclohexyl-1,3-dioxane(12 mmol), 50 ml of toluene and 10 ml of formic acid was refluxed for 30minutes. The solution was cooled to room temperature, and then washedthree times with 30 ml of water. The solvent was removed under reducedpressure, and the residue was then purified through columnchromatography (toluene) to obtain(4-(4-(4-propylphenyl)difluoromethoxy)phenyl)cyclohexanecarboaldehyde(10 mmol).

To a mixture of(4-(4-(4-propylphenyl)difluoromethoxy)phenyl)cyclohexanecarboaldehyde(10 mmol), triphenylphosphine (11 mmol) and 40 ml of dry DMF, 30 ml of aDMF solution containing sodium chlorodifluoroacetate (12 mmol) was addeddropwise at about 80° C. After the completion of the dropping, thesolution was cooled to room temperature, 50 ml of toluene was added,followed by extraction. The solvent was removed, and the resultingresidue was purified by column chromatography (a toluene-heptane mixingsolvent) and then recrystallization (ethanol-benzene) to obtain thedesired compound (6 mmol) Its structure was properly supported byspectrum data.

In accordance with the procedure of Example 6, the compounds representedby the following formula (1-4-5) were prepared.

Typically, the compounds shown in Tables 20 and 21 were prepared.

TABLE 20 Z₂ R₁ m X CF₂O C₂H₅ 0 H CF₂O C₃H₇ 0 H CF₂O C₂H₅ 0 F CF₂O C₃H₇ 0F CF₂O C₂H₅ 2 F CF₂O C₃H₇ 2 F CF₂O C₅H₁₁ 2 F CF₂O C₃H₇ 4 F OCF₂ C₂H₅ 0 HOCF₂ C₃H₇ 0 H OCF₂ C₂H₅ 0 F OCF₂ C₃H₇ 0 F OCF₂ C₂H₅ 2 F OCF₂ C₃H₇ 2 FOCF₂ C₅H₁₁ 2 F OCF₂ C₃H₇ 4 F p = 0

TABLE 21 Z₂

R₁ m X CF₂O

C₃H₇ 0 F CF₂O

C₃H₇ 2 F CF₂O

C₃H₇ 0 F CF₂O

C₃H₇ 0 F CF₂O

C₃H₇ 0 F CF₂O

C₃H₇ 0 F CF₂O

C₃H₇ 2 F CF₂O

C₃H₇ 0 F CF₂O

C₃H₇ 0 F OCF₂O

C₃H₇ 0 F OCF₂O

C₃H₇ 2 F OCF₂O

C₃H₇ 0 F OCF₂O

C₃H₇ 0 F OCF₂O

C₃H₇ 0 F OCF₂O

C₃H₇ 0 F OCF₂O

C₃H₇ 2 F OCF₂O

C₃H₇ 0 F OCF₂O

C₃H₇ 0 F p = 1

Example 7

Preparation of4-(2-methyl-2-(4-propylcyclohexyl)ethenyl)-1-(2,2-difluoroethenyl)cyclohexane[a compound of the general formula (1) in which R₁=a propyl group, aring C=1,4-cyclohexylene, Z₃=—CR₂═CH—, R₂=a methyl group, p=q=0, m=0,and X=a fluorine atom]

To a mixture of4-(2-methyl-2-(4-propylcyclohexyl)ethenyl)cyclohexanecarboaldehyde (20mmol) prepared in accordance with a process of Example 4,triphenylphosphine (22 mmol) and 100 ml of dry DMF, 70 ml of a DMFsolution containing sodium chlorodifluoroacetate (23 mmol) was addeddropwise at about 100° C. After the completion of the dropping, thesolution was stirred for 30 minutes, while the same temperature wasmaintained. After the solution was cooled to room temperature, 100 ml oftoluene was added, followed by extraction. The solvent was removed, andthe resulting residue was purified by column chromatography (atoluene-heptane mixing solvent) and then recrystallization(ethanol-benzene) to obtain the desired compound (15 mmol). Itsstructure was properly supported by spectrum data.

In accordance with the procedure of Example 7, the compounds representedby the following formula (1-4-6) were prepared.

Typically, the compounds shown in Tables 22 to 24 were prepared.

TABLE 22

R₁ R₂ m X

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 2 F

C₃H₇ C₂H₅ 0 F

CH₃ 0 F

C₃H₇ CH₃ 0 F

C₃H₇ 2 F p = q = 0

TABLE 23

R₁ R₂ m X

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 2 F

C₃H₇ CH₃ 0 F

CH₃ 0 F

CH₃ 0 F p = 1, q = 0

TABLE 24

R₁ R₂ m X

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 2 F

C₃H₇ CH₃ 4 F

C₅H₁₁ C₂H₅ 0 F

C₃H₇ CH₃ 0 F

CH₃ 0 F

CH₃ 0 F p = 0, q = 1

In accordance with the procedure of Example 7, the compounds representedby the following formula (1-4-7) were prepared.

Typically, the compounds shown in Tables 25 to 27 were prepared.

TABLE 25

R₁ R₂ m X

C₃H₇ CH₃ 0 H

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 2 F

C₃H₇ C₂H₅ 0 F

CH₃ 0 F

C₃H₇ CH₃ 0 F

C₃H₇ 2 F p = q = 0

TABLE 26

R₁ R₂ m X

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 2 F

C₃H₇ CH₃ 0 F

CH₃ 0 F

CH₃ 0 F p = 1, q = 0

TABLE 27

R₁ R₂ m X

C₃H₇ CH₃ 0 F

C₃H₇ CH₃ 2 F

C₃H₇ CH₃ 4 F

C₅H₁₁ C₂H₅ 0 F

C₃H₇ CH₃ 0 F

CH₃ 0 F

CH₃ 0 F p = 0, q = 1

In accordance with the procedure of Examples 1 to 7, the compoundsrepresented by the above formula (1) were prepared.

Typically, the compounds shown in Tables 28 to 32 were prepared.

TABLE 28

Z₃ R₁ m  X

C₃H₇ 0 H

C₃H₇ 0 F

C₃H₇ 0 F

C₃H₇ 2 F

2 F

C₃H₇ 0 F

C₅H₁₁ 0 F

C₃H₇ 0 H

C₃H₇ 0 F

C₃H₇ 0 F

C₃H₇ 2 F

2 F

C₃H₇ 0 F

C₅H₁₁ 0 F p = q = 0 TABLE 29

Z₃ R₁ m  X

C₃H₇ 0 H

C₃H₇ 0 F

C₃H₇ 0 F

C₃H₇ 2 F

2 F

C₃H₇ 0 F

C₅H₁₁ 0 F

C₃H₇ 0 H

C₃H₇ 0 F

C₃H₇ 0 F

C₃H₇ 2 F

2 F

C₃H₇ 0 F

C₅H₁₁ 0 F p = q = 0 TABLE 30

R₁ Z₂ Z₃ m X

C₃H₇ —

0 F

C₃H₇ —

2 F

C₃H₇ —

0 F

—

0 F

C₃H₇ —

0 F

C₃H₇ —

0 F

C₃H₇ —

2 F

C₃H₇ —

0 F

—

0 F

C₃H₇ —

0 F p = 0, q = 1

TABLE 31

R₁ Z₂ Z₃ m X

C₃H₇ —

0 F

C₃H₇ —

2 F

C₃H₇ —

0 F

—

0 F

C₃H₇ —

0 F

C₃H₇ —

0 F

C₃H₇ —

2 F

C₃H₇ —

0 F

—

0 F

C₃H₇ —

0 F p = 0, q = 1

TABLE 32

R₁ Z₁ Z₂ Z₃ m X

C₃H₇ — —

0 F

— —

0 F

— —

0 F

C₃H₇ — —

0 F

— —

0 F

— —

0 F

C₃H₇ — —

0 F

— —

0 F

— —

0 F

C₃H₇ — —

0 F

— —

0 F

— —

0 F p = 1

Examples of compositions prepared by the use of the compoundsrepresented by the general formula (1) of the present invention will bedescribed.

However, the compounds which can be used in the 25 examples arerepresented by symbols which are defined in Table 33 given below. Forexample, when the hydrogen atoms of trans-1,4-cyclohexylene in thefollowing partial structural formula (w) are substituted by deuterium atpositions Q₁, Q₂ and Q₃, it is represented by a symbol H[1D,2D,3D].Moreover, when the hydrogen atoms of trans-1,4-cyclohexylene aresubstituted by deuterium at positions Q₅, Q₆ and Q₇, it is representedby a symbol H[5D,6D,7D]. Thus, the substitution positions of deuteriumare shown by the numbers in the brackets [ ].

TABLE 33 Representation of Compounds by Use of Symbols R—(A₁)—Z₁— . . .—Z_(n)—(A_(n))—X 1) Left Terminal Group R— Symbol C_(n)H_(2n+1)— n—C_(n)H_(2n+1)O— nO— C_(n)H_(2n+1)OC_(m)H_(2m)— nOm— CH₂═CH— V—CH₂═CHC_(n)H_(2n)— Vn— C_(n)H_(2n+1)CH═CHC_(m)H_(2m)— nVm—C₂H_(2n+1)CH═CHC_(m)H_(2m)CH═CHC_(k)H_(2k)— nVmVk— 2) Ring Structure—(A₁)—, (A_(n))— Symbol

B

B(F)

B(2F,3F)

B(F,F)

H

Py

D

Ch 3) Bond Group —Z₁—, —Z_(n)— Symbol —C₂H₄— 2 —C₄H₈— 4 —COO— E —C≡C— T—CH═CH— V —CF₂O— CF2O —OCF₂— OCF2 —CF═CF— FVF

V(Me) 4) Right Terminal Group —X Symbol —F —F —Cl —CL —CN —C —CF₃ —CF3—OCF₃ —OCF3 —OCF₂H —OCF2H —C_(n)H_(2n+1) —n —OC_(n)H_(2n+1) —On —COOCH₃—EMe —C_(n)H_(2n)CH═CH₂ —nV —C_(m)H_(2m)CH═CHC_(n)H_(2n+1) —mVn—C_(m)H_(2m)CH═CHC_(n)H_(2n)F —mVnF —CH═CF₂ —VFF —C_(n)H_(2n)CH═CF₂—nVFF —C≡C═CN —TC 5) Examples of Representation Ex. 1 3-H2B(F,F)B(F)—F

Ex. 2 3-HB(F)TB-2

Ex. 3 IV2-BEB(F,F)—C

Incidentally, T_(NI) is a temperature at a clearing point; a viscosity ηwas measured at 20° C.; and an optical anisotropy Δn, a dielectricanisotropy Δε, a threshold voltage V_(th) and a pitch length P ofhelical twist were measured at 25° C., respectively. In addition, % isbased on weight.

Example 8

TABLE 34 5-HB(2F,3F)H—VFF 5.0% 1V2-BEB(F,F)—C 5.0% 3-HB—C 25.0% 1-BTB-35.0% 2-BTB-1 10.0% 3-HH-4 11.0% 3-HHB-1 11.0% 3-HHB-3 4.0% 3-H2BTB-24.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 6.0% 3-HB(F)TB-3 6.0%CM33 0.8 part T_(NI) = 87.5 (° C.) η = 15.5 (mPa · s) Δn = 0.162 Δ_(ε) =7.0 Vth = 2.11 (V) P = 11 μm

Example 9

TABLE 35 5-HBBH—VFF 3.0% V2-HB—C 12.0% 1V2-HB—C 12.0% 3-HB—C 15.0%3-H[1D,2D,3D]—C 9.0% 3-HB(F)—C 5.0% 2-BTB-1 2.0% 3-HH-4 8.0% 3-HH—VFF6.0% 2-H[1D,2D,3D]HB—C 3.0% 3-HHB—C 6.0% 3-HB(F)TB-2 8.0% 3-H2BTB-2 5.0%3-H2BTB-3 2.0% 3-H2BTB-4 4.0% T_(NI) = 91.2 (° C.) η = 17.7 (mPa · s) Δn= 0.152 Δ_(ε) = 8.8 Vth = 1.98 (V)

Example 10

TABLE 36 5-HB(2F,3F)H—VFF 4.0% 5-HBBH—VFF 4.0% 2O1-BEB(F)—C 5.0%3O1-BEB(F)—C 15.0% 4O1-BEB(F)—C 13.0% 5O1-BEB(F)—C 13.0% 2-HHB(F)—C15.0% 3-HHB(F)—C 15.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0% 3-HHB-1 4.0%3-HHB—O1 4.0% T_(NI) = 92.5 (° C.) η = 87.9 (mPa · s) Δn = 0.147 Δ_(ε) =31.0 Vth = 0.86 (V)

Example 11

TABLE 37 3-BBHH—2VFF 2.0% 3-BH2H—VFF 3.0% 5-PyB—F 4.0% 3-PyB(F)—F 4.0%2-BB—C 5.0% 4-BB—C 4.0% 5-BB—C 5.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-22.0% 6-PyB—O5 3.0% 6-PyB—O6 3.0% 6-PyB—O7 3.0% 6-PyB—O8 3.0% 3-PyBB—F6.0% 4-PyBB—F 6.0% 5-PyBB—F 6.0% 3-HHB-1 6.0% 3-HHB-3 8.0% 2-H2BTB-24.0% 2-H2BTB-3 4.0% 2-H2BTB-4 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0% T_(NI)= 94.4 (° C.) η = 36.5 (mPa · s) Δn = 0.197 Δ_(ε) = 6.5 Vth = 2.26 (V)

Example 12

TABLE 38 V—HBH—VFF 3.0% 3-DB—C 10.0% 4-DB—C 10.0% 2-BEB—C 12.0% 3-BEB—C4.0% 3-PyB(F)—F 6.0% 3-HEB—O4 8.0% 4-HEB—O2 6.0% 5-HEB—O1 6.0% 3-HEB—O25.0% 5-HEB—O2 4.0% 5-HEB-5 5.0% 4-HEB-5 5.0% 1O—BEB-2 4.0% 3-HHB-1 3.0%3-HHEBB—C 3.0% 3-HBEBB—C 3.0% 5-HBEBB—C 3.0% T_(NI) = 68.4 (° C.) η =39.5 (mPa · s) Δn = 0.121 Δ_(ε) = 11.5 Vth = 1.30 (V)

Example 13

TABLE 39 3-HVH—2VFF 4.0% V2-HBBH—VFF 2.0% 3-HB—C 18.0% 7-HB—C 3.0%1O1-HB—C 10.0% 3-HB(F)—C 10.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0%1O1-HH-3 3.0% 2-BTB—O1 7.0% 3-HHB-1 7.0% 3-HHB—F 4.0% 3-HHB—O1 4.0%3-HHB-3 6.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0%3-PyBB-2 3.0% T_(NI) = 81.9 (° C.) η = 18.1 (mPa · s) Δn = 0.143 Δ_(ε) =8.2 Vth = 1.74 (V)

Example 14

TABLE 40 3-BHVH—VFF 3.0% 5-HVHH—VFF 3.0% V—HV(Me)H—VFF 4.0% 2O1-BEB(F)—C5.0% 3O1-BEB(F)—C 12.0% 5O1-BEB(F)—C 4.0% 1V2-BEB(F,F)—C 10.0% 3-HH—EMe10.0% 3-HB—O2 14.0% 7-HEB—F 2.0% 3-HHEB—F 2.0% 5-HHEB—F 2.0% 3-HBEB—F4.0% 2O1-HBEB(F)—C 2.0% 3-HB(F)EB(F)—C 2.0% 3-HBEB(F,F)—C 2.0% 3-HHB—F4.0% 3-HHB—O1 4.0% 3-HHB-3 7.0% 3-HEBEB—F 2.0% 3-HEBEB-1 2.0% T_(NI) =76.8 (° C.) η = 35.7 (mPa · s) Δn = 0.114 Δ_(ε) = 23.4 Vth = 0.99 (V)

Example 15

TABLE 41 3-BFVFB—VFF 4.0% 5-BEB(F)—C 5.0% V-HB—C 11.0% 5-PyB—C 6.0%4-BB-3 7.0% 3-HH—2V 10.0% 5-HH—V 11.0% V-HHB-1 7.0% V2-HHB-1 15.0%3-HHB-1 9.0% 1V2-HBB-2 10.0% 3-HHEBH-3 5.0% T_(NI) = 95.2 (° C.) η =15.7 (mPa · s) Δn = 0.123 Δ_(ε) = 4.8 Vth = 2.36 (V)

Example 16

TABLE 42 3-BCF2OBH—2VFF 2.0% 3-BD2H—VFF 3.0% 2O1-BEB(F)—C 5.0%3O1-BEB(F)—C 12.0% 5O1-BEB(F)—C 4.0% 1V2-BEB(F,F)—C 16.0% 3-HB—O2 10.0%3-HH-4 3.0% 3-HHB—F 3.0% 3-HHB-1 8.0% 3-HHB—O1 4.0% 3-HBEB—F 2.0%3-HHEB—F 4.0% 5-HHEB—F 7.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0%3-HB(F)TB-2 5.0% T_(NI) = 89.2 (° C.) η = 40.2 (mpa · s) Δn = 0.143Δ_(ε) = 28.0 Vth = 1.01 (V)

Example 17

TABLE 43 3-HVH—VF 5.0% 2-BEB—C 12.0% 3-BEB—C 4.0% 4-BEB—C 6.0% 3-HB—C28.0% 3-HEB—O4 7.0% 4-HEB—O2 8.0% 5-HEB—O1 8.0% 3-HEB—O2 6.0% 5-HEB—O25.0% 3-HHB-1 7.0% 3-HHB—O1 4.0% T_(NI) = 63.5 (° C.) η = 24.2 (mPa · s)Δn = 0.112 Δ_(ε) = 10.0 Vth = 1.35 (V)

Example 18

TABLE 44 3-BB(F)BH—VFF 3.0% 2-BEB—C 10.0% 5-BB—C 12.0% 7-BB—C 7.0%1-BTB-3 7.0% 2-BTB-1 10.0% 1O—BEB-2 10.0% 1O—BEB-5 12.0% 2-HHB-1 4.0%3-HHB—F 4.0% 3-HHB-1 7.0% 3-HHB—O1 4.0% 3-HHB-3 10.0% T_(NI) = 69.3 (°C.) η = 20.9 (mPa · s) Δn = 0.164 Δ_(ε) = 6.5 Vth = 1.78 (V)

Example 19

TABLE 45 3-B(F)B(F)2H—2VFF 4.0% V2-HBBH—VFF 3.0% 1V2-BEB(F,F)—C 8.0%3-HB—C 10.0% V2V—HB—C 14.0% V2V—HH-3 19.0% 3-HB—O2 4.0% 3-HHB-1 10.0%3-HHB-3 12.0% 3-HB(F)TB-2 2.0% 3-HB(F)TB-3 4.0% 3-H2BTB-2 2.0% 3-H2BTB-34.0% 3-H2BTB-4 4.0% T_(NI) = 98.5 (° C.) η = 18.5 (mPa · s) Δn = 0.124Δ_(ε) = 7.7 Vth = 2.13 (V)

Example 20

TABLE 46 5-HB(2F,3F)H—VFF 5.0% 5-BTB(F)TB-3 10.0% V2-HB—TC 10.0% 3-HB—TC10.0% 3-HB—C 10.0% 5-HB—C 7.0% 5-BB—C 3.0% 2-BTB-1 10.0% 2-BTB—O1 5.0%3-HH-4 5.0% 3-HHB-1 10.0% 3-HHB-3 6.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0%3-HB(F)TB-2 3.0% T_(NI) = 97.3 (° C.) η = 14.9 (mPa · s) Δn = 0.205Δ_(ε) = 6.7 Vth = 2.12 (V)

Example 21

TABLE 47 5-HB(2F,3F)H—VFF 5.0% 5-HBBH—VFF 4.0% 1V2-BEB(F,F)—C 6.0%3-HB—C 18.0% 2-BTB-1 10.0% 5-HH—VFF 25.0% 1-BHH—VFF 4.0% 1-BHH—2VFF11.0% 3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HHB-1 4.0% T_(NI) =86.3 (° C.) η = 14.3 (mPa · s) Δn = 0.136 Δ_(ε) = 6.6 Vth = 2.05 (V)

Example 22

TABLE 48 5-HB(2F,3F)H—VFF 4.0% 3-HVH—VF 4.0% 2-HB—C 5.0% 3-HB—C 12.0%3-HB—O2 11.0% 2-BTB-1 3.0% 3-HHB-1 8.0% 3-HHB—F 4.0% 3-HHB—O1 5.0%3-HHB-3 10.0% 3-HHEB—F 4.0% 5-HHEB—F 4.0% 2-HHB(F)—F 7.0% 3-HHB(F)—F7.0% 5-HHB(F)—F 7.0% 3-HHB(F,F)—F 5.0% T_(NI) = 99.8 (° C.) η = 18.7(mPa · s) Δn = 0.101 Δ_(ε) = 4.4 Vth = 2.60 (V)

Example 23

TABLE 49 5-HB(2F,3F)H—VFF 5.0% 2-HHB(F)—F 15.0% 3-HHB(F)—F 15.0%5-HHB(F)—F 15.0% 2-H2HB(F)—F 10.0% 3-H2HB(F)—F 5.0% 5-H2HB(F)—F 10.0%2-HBB(F)—F 6.0% 3-HBB(F)—F 6.0% 5-HBB(F)—F 13.0% CN 0.3 part T_(NI) =97.4 (° C.) η = 26.1 (mPa · s) Δn = 0.095 Δ_(ε) = 5.0 Vth = 2.22 (V) P =79 μm

Example 24

TABLE 50 3-BH2H—VFF 4.0% 7-HB(F)—F 5.0% 5-H2B(F)—F 5.0% 3-HB—O2 10.0%3-HH-4 2.0% 3-HH[5D,6D,7D]-4 3.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0%5-HH[5D,6D,7D]B(F)—F 10.0% 3-H2HB(F)—F 5.0% 2-HBB(F)—F 3.0% 3-HBB(F)—F3.0% 5-HBB(F)—F 6.0% 2-H2BB(F)—F 5.0% 3-H2BB(F)—F 6.0% 3-HHB-1 4.0%3-HHB—O1 5.0% 3-HHB-3 4.0% T_(NI) = 87.0 (° C.) η = 18.7 (mPa · s) Δn =0.092 Δ_(ε) = 3.3 Vth = 2.65 (V)

Example 25

TABLE 51 3-B(F)B(F)2H—2VFF 4.0% 7-HB(F,F)—F 3.0% 3-HB—O2 7.0% 2-HHB(F)—F10.0% 3-HHB(F)—F 10.0% 5-HHB(F)—F 10.0% 2-HBB(F)—F 9.0% 3-HBB(F)—F 9.0%5-HBB(F)—F 16.0% 2-HBB—F 2.0% 3-HBB—F 2.0% 5-HBB—F 3.0% 3-HBB(F,F)—F5.0% 5-HBB(F,F)—F 10.0% T_(NI) = 84.2 (° C.) η = 25.6 (mPa · s) Δn =0.113 Δ_(ε) = 5.7 Vth = 2.01 (V)

Example 26

TABLE 52 3-BCF2OBH—2VFF 3.0% 3-BFVFB—VFF 4.0% 7-HB(F,F)—F 3.0%3-H2HB(F,F)—F 12.0% 4-H2HB(F,F)—F 10.0% 5-H2HB(F,F)—F 10.0% 3-HHB(F,F)—F5.0% 4-HHB(F,F)—F 5.0% 3-HH2B(F,F)—F 15.0% 5-HH2B(F,F)—F 10.0%3-HBB(F,F)—F 12.0% 5-HBB(F,F)—F 5.0% 3-HBCF2OB(F,F)—F 6.0% T_(NI) = 74.8(° C.) η = 22.2 (mPa · s) Δn = 0.093 Δ_(ε) = 8.3 Vth = 1.58 (V)

Example 27

TABLE 53 3-BD2H—VFF 5.0% 3-BBHH—2VFF 3.0% 7-HB(F,F)—F 5.0% 3-H2HB(F,F)—F12.0% 4-H2HB(F,F)—F 10.0% 3-HHB(F,F)—F 10.0% 4-HHB(F,F)—F 5.0%3-HBB(F,F)—F 10.0% 3-HHEB(F,F)—F 10.0% 4-HHEB(F,F)—F 3.0% 5-HHEB(F,F)—F3.0% 2-HBEB(F,F)—F 3.0% 3-HBEB(F,F)—F 5.0% 5-HBEB(F,F)—F 3.0%3-HDB(F,F)—F 10.0% 3-HHBB(F,F)—F 3.0% T_(NI) = 78.4 (° C.) η = 36.2 (mPa· s) Δn = 0.088 Δ_(ε) = 12.5 Vth = 1.42 (V)

Example 28

TABLE 54 3-BB(F)BH—VFF 4.0% 3-HVH—2VFF 3.0% 3-HB—CL 10.0% 5-HB—CL 4.0%7-HB—CL 4.0% 1O1-HH-5 2.0% 2-HBB(F)—F 8.0% 3-HBB(F)—F 8.0% 5-HBB(F)—F14.0% 4-HHB—CL 8.0% 5-HHB—CL 8.0% 3-H2HB(F)—CL 4.0% 3-HBB(F,F)—F 10.0%5-H2BB(F,F)—F 9.0% 3-HB(F)VB-2 2.0% 3-HB(F)VB-3 2.0% T_(NI) = 92.8 (°C.) η = 20.9 (mPa · s) Δn = 0.129 Δ_(ε) = 4.9 Vth = 2.32 (V)

Example 29

TABLE 55 5-HBBH—VFF 4.0% 3-HHB(F,F)—F 9.0% 3-H2HB(F,F)—F 8.0%4-H2HB(F,F)—F 8.0% 5-H2HB(F,F)—F 8.0% 3-HBB(F,F)—F 21.0% 5-HBB(F,F)—F20.0% 3-H2BB(F,F)—F 10.0% 5-HHBB(F,F)—F 3.0% 5-HHEBB—F 2.0%3-HH2BB(F,F)—F 3.0% 1O1-HBBH-4 2.0% 1O1-HBBH-5 2.0% T_(NI) = 97.6 (° C.)η = 33.7 (mPa · s) Δn = 0.116 Δ_(ε) = 9.2 Vth = 1.74 (V)

Example 30

TABLE 56 5-HBBH—VFF 2.0% 5-HVHH—VFF 2.0% V—HV(Me)H—VFF 2.0% 5-HB—F 12.0%6-HB—F 9.0% 7-HB—F 5.0% 2-HHB—OCF3 5.0% 3-HHB—OCF3 7.0% 4-HHB—OCF3 7.0%5-HHB—OCF3 5.0% 3-HH2B—OCF3 4.0% 5-HH2B—OCF3 4.0% 3-HHB(F,F)-OCF3 5.0%3-HBB(F)—F 10.0% 5-HBB(F)—F 10.0% 3-HH2B(F)—F 3.0% 3-HB(F)BH-3 2.0%5-HBBH-3 2.0% 3-HHB(F,F)—OCF2H 4.0% T_(NI) = 88.7 (° C.) η = 15.2 (mPa ·s) Δn = 0.093 Δ_(ε) = 4.5 Vth = 2.40 (V)

Example 31

TABLE 57 V2-HBBH—VFF 2.0% V—HBH—VFF 3.0% 3-BHVH—VFF 2.0% 5-H4HB(F,F)—F7.0% 5-H4HB—OCF3 10.0% 3-H4HB(F,F)—CF3 8.0% 5-H4HB(F,F)—CF3 10.0%3-HB—CL 6.0% 5-HB—CL 4.0% 2-H2BB(F)—F 5.0% 3-H2BB(F)—F 10.0%5-HVHB(F,F)—F 5.0% 3-HHB—OCF3 3.0% 3-H2HB—OCF3 5.0% V—HHB(F)—F 5.0%3-HHB(F)—F 5.0% 5-HHEB—OCF3 2.0% 3-HBEB(F,F)—F 5.0% 5-HH—V2F 3.0% T_(NI)= 3.8 (° C.) η = 26.1 (mPa · s) Δn = 0.099 Δ_(ε) = 8.3 Vth = 1.75 (V)

Example 32

TABLE 58 5-HBBH—VFF 4.0% 5-HB(2F,3F)H—VFF 2.0% 2-HHB(F)—F 2.0%3-HHB(F)—F 2.0% 5-HHB(F)—F 2.0% 2-HBB(F)—F 6.0% 3-HBB(F)—F 6.0%5-HBB(F)—F 10.0% 2-H2BB(F)—F 9.0% 3-H2BB(F)—F 9.0% 3-HBB(F,F)—F 25.0%5-HBB(F,F)—F 19.0% 1O1-HBBH-4 2.0% 1O1-HBBH-5 2.0% T_(NI) = 92.0 (° C.)η = 33.3 (mPa · s) Δn = 0.136 Δ_(ε) = 7.4 Vth = 1.90 (V)

Example 33

TABLE 59 3-HVH—VF 3.0% 3-BFVFB—VFF 3.0% 5-HB—CL 12.0% 3-HH-4 4.0%3-HB—O2 20.0% 3-H2HB(F,F)—F 8.0% 3-HHB(F,F)—F 8.0% 3-HBB(F,F)—F 6.0%2-HHB(F)—F 5.0% 3-HHB(F)—F 5.0% 5-HHB(F)—F 5.0% 2-H2HB(F)—F 2.0%3-H2HB(F)—F 1.0% 5-H2HB(F)—F 2.0% 3-HHBB(F,F)—F 4.0% 3-HBCF2OB—OCF3 4.0%5-HBCF2OB(F,F)—CF3 4.0% 3-HHB-1 2.0% 3-HHB—O1 2.0% T_(NI) = 69.2 (° C.)η = 13.9 (mPa · s) Δn = 0.090 Δ_(ε) = 4.1 Vth = 2.21 (V)

Example 34

TABLE 60 3-HVH—VF 10.0% 3-HVH—2VFF 10.0% 3-BHVH—VFF 10.0% 3-BH2H—VFF10.0% V2-HBBH—VFF 2.0% 1V2-BEB(F,F)—C 5.0% 3-HB—C 25.0% 1-BTB-3 3.0%3-HH-4 2.0% 3-HHB-1 3.0% 3-H2BTB-2 2.0% 3-H2BTB-3 2.0% 3-H2BTB-4 4.0%3-HB(F)TB-2 6.0% 3-HB(F)TB-3 6.0% T_(NI) = 91.9 (° C.) η = 15.8 (mPa ·s) Δn = 0.138 Δ_(ε) = 6.7 Vth = 2.16 (V)

What is claimed is:
 1. A fluorovinyl derivative compound represent bythe general formula (1)

wherein R₁ is an alkyl group having 1 to 18 carbon atoms, and amethylene group in the alkyl group may be substituted by an oxygen atom,a sulfur atom, —CH═CH— or —C≡C— and a hydrogen atom in the alkyl groupmay be substituted by a halogen atom or a cyano group; rings A, B and Care each independently 1,4-cyclohexylene, 1,4-cyclohexenylene,1,4-phenylene, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl orpyrimidine-2,5-diyl in which a hydrogen atom in the ring may besubstituted by a halogen atom; Z₁, Z₂ and Z₃ are each independently asingle bond, —CH₂CH₂—, —CH═CH—,-CH₂O—, —OCH₂—, —(CH₂)₄—, —(CH₂)₃—O—,—O—(CH₂)₃—, —(CH₂)₂—CH═CH—, —CH═CH—(CH₂)₂—, —CF₂O—, —OCF₂—, —CR₂═CH—,—CH═CR₂— or —CF═CF—, and R₂ is an alkyl group having 1 to 5 carbonatoms; X is a hydrogen atom or a fluorine atom; p and q are eachindependently 0 or 1; and m is an integer of 0 to 5; except for (1) acompound in which p is 0, q is 0, Z₃ is the single bond, —CH₂CH₂—,—CH₂O— or —OCH₂—, and the ring C is 1,4-cyclohexylene or 1,4-phenylene,(2) a compound in which p is 0, q is 1, Z₂ and Z₃ are each the singlebond, the ring B is 1,4-phenylene, and the ring C is 1,4-cyclohexyleneor 1,4-phenylene, and (3) a compound in which p is 0, is 1, Z₂ is asingle bond, Z₃ is —CH₂CH₂—, the ring B is 1,4-phenylene, the ring C is1,4-cyclohexylene, and X is a hydrogen atom.
 2. The fluorovinylderivative compound according to claim 1 wherein at least one of Z₁, Z₂and Z₃ is —CH═CH—, —(CH₂)₃O—, —O—(CH₂)₃—, —(CH₂)₂—CH═CH—,—CH═CH—(CH₂)₂—, —CF₂O—, —OCF₂—, —CR₂═CH—, —CH═CR₂— or —CF═CF—; and R₂ isan alkyl group having 1 to 5 carbon atoms.
 3. The fluorovinyl derivativecompound according to claim 1 wherein at least one of Z₁, Z₂ and Z₃ is—CH═CH—, —(CH₂)₂—CH═CH—, —CH═CH—(CH₂)₂— or —CF═CF—.
 4. The fluorovinylderivative compound according to claim 1 wherein at least one of Z₁, Z₂and Z₃ is —(CH₂)₃—O—, —O—(CH₂)₃—, —CF₂O— or —OCF₂—.
 5. The fluorovinylderivative compound according to claim 1 wherein at least one of Z₁, Z₂and Z₃ is —CR₂═CH— or —CH═CR₂—; and R₂ is an alkyl group having 1 to 5carbon atoms.
 6. A fluorovinyl derivative compound represented by thegeneral formula (1-1)

wherein R₁, X and m are as defined in claim 1; Z₁, Z₂ and Z₃ are eachindependently a single bond, —CH₂CH₂—, —CH₂O—, —OCH₂— or —(CH₂)₄—; andrings A, B and C are each independently 1,4-cyclohexylene or1,4-phenylene in which a hydrogen atom in the ring may be substituted bya halogen atom.
 7. A fluorovinyl derivative compound represented by thegeneral formula (1-2)

wherein R₁, X and m are as defined in claim 1; r and s are eachindependently 0 or 1; and L₁, L₂, L₃ and L₄ are each independently ahydrogen atom or a fluorine atom.
 8. The fluorovinyl derivative compoundaccording to claim 7 wherein r+s is 1 or
 0. 9. The fluorovinylderivative compound according to claim 7 wherein r+s is
 2. 10. Afluorovinyl derivative compound represented by the general formula (1-3)

wherein R₁, X, m, L₁, L₂, L₃ and L₄ are as defined in claim 7; Z₂ and Z₃are each independently a single bond, —CH₂CH₂—, —CH₂O—, —OCH₂— or—(CH₂)₄—, and Z₂ and Z₃ are not simultaneously the single bonds; and aring C is 1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom inthe ring may be substituted by a halogen atom.
 11. The fluorovinylderivative compound according to claim 10 wherein the ring C is1,4-cyclohexylene.
 12. The fluorovinyl derivative compound according toclaim 10 wherein the ring C is 1,4-phenylene in which a hydrogen atom inthe ring may be substituted by a halogen atom.
 13. A fluorovinylderivative compound represented by the general formula (1-1-1)

wherein R₁, X and m are as defined in claim 1; and L₁ to L₈ are eachindependently a hydrogen atom or a fluorine atom.
 14. A fluorovinylderivative compound represented by the general formula (1-1-2)

wherein R₁, X and m are as defined in claim 1; L₁ to L₁₂ are eachindependently a hydrogen atom or a fluorine atom; and r is 0 or
 1. 15. Afluorovinyl derivative compound represented by the general formula(1-1-3)

wherein R₁, X and m are as defined in claim 1; L₁ to L₈ are eachindependently a hydrogen atom or a fluorine atom; and r is 0 or
 1. 16. Afluorovinyl derivative compound represented by the general formula(1-4-1)

wherein R₁, X and m are as defined in claim 1; and the ring C is1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom in the ringmay be substituted by a halogen atom.
 17. A fluorovinyl derivativecompound represented by the general formula (1-4-2)

wherein R₁, X and m are as defined in claim 1; and the rings B and C areeach 1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom in thering may be substituted by a halogen atom.
 18. A fluorovinyl derivativecompound represented by the general formula (1-4-3)

wherein R₁, X and m are as defined in claim 1; and the rings B and C areeach 1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom in thering may be substituted by a halogen atom.
 19. A fluorovinyl derivativecompound represented by the general formula (1-4-4)

wherein R₁, X, m, Z, and p are as defined in claim 1; and the ring A is1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom in the ringmay be substituted by a halogen atom.
 20. A fluorovinyl derivativecompound represented by the general formula (1-4-5)

wherein R₁, X, m, Z₁ and p are as defined in claim 1; the ring A is1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom in the ringmay be substituted by a halogen atom; and Z₂ is —CF₂O— or —OCF₂—.
 21. Afluorovinyl derivative compound represented by the general formula(1-4-6)

wherein R₁, X, m, Z₁, Z₃, p and q are as defined in claim 1; the ringsA, B and C are each 1,4-cyclohexylene or 1,4-phenylene in which ahydrogen atom in the ring may be substituted by a halogen atom; and R₂is an alkyl group having 1 to 5 carbon atoms.
 22. A fluorovinylderivative compound represented by the general formula (1-4-7)

wherein R₁, X, m, Z₁, Z₃, p and q are as defined in claim 1; the ringsA, B and C are each 1,4-cyclohexylene or 1,4-phenylene in which ahydrogen atom in the ring may be substituted by a halogen atom; and R₂is an alkyl group having 1 to 5 carbon atoms.
 23. A liquid crystalcomposition which contains at least one of the liquid crystal compoundsdescribed in claim
 1. 24. A liquid crystal composition which contains,as a first component, at least one of the liquid crystal compoundsdescribed in claim 1, and as a second component, at least one compoundselected from the group consisting of compounds of the general formulae(2), (3) and (4)

wherein R₃ is an alkyl group having 1 to 10 carbon atoms, and anoptional unadjacent methylene group in the alkyl group may besubstituted by an oxygen atom or —CH═CH—, and an optional hydrogen atomin the alkyl group may be substituted by a fluorine atom; Y₁ is afluorine atom, a chlorine atom, OCF₃, OCF₂H, CF₃, CF₂H, CFH₂, OCF₂CF₂Hor OCF₂CFHCF₃; L₁₃ and L₁₄ are each independently a hydrogen atom or afluorine atom; Z₄ and Z₅ are each independently a 1,2-ethylene group, a1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, —CH═CH— or a single bond; aring D is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylenein which a hydrogen atom may be substituted by a halogen atom; and aring E is trans-1,4-cyclohexylene or 1,4-phenylene in which a hydrogenatom may be substituted by a fluorine atom.
 25. A liquid crystalcomposition which contains, as a first component, at least one of theliquid crystal compounds described in claim 1, and as a secondcomponent, at least one compound selected from the group consisting ofcompounds of the general formulae (5) and (6)

wherein R₄ and R₅ are each independently an alkyl group having 1 to 10carbon atoms, and an optional unadjacent methylene group in the alkylgroup may be substituted by an oxygen atom or —CH═CH—, and an optionalhydrogen atom in the alkyl group may be substituted by a fluorine atom;Y₂ is a —CN group or —C≡C—CN; a ring F is trans-1,4-cyclohexylene,1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; a ring G istrans-1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl in which ahydrogen atom may be substituted by a fluorine atom; a ring M istrans-1,4-cyclohexylene or 1,4-phenylene; Z₆ is a 1,2-ethylene group,—COO— or a single bond; L₁₅, L₁₆ and L₁₇ are each independently ahydrogen atom or a fluorine atom; and b, c and d are each independently0 or
 1. 26. A liquid crystal composition which contains at least one ofthe liquid crystal compounds described in claim 1 as a first component,at least one compound selected from the group consisting of compounds ofthe following general formulae (2), (3) and (4) as a second component

wherein R₃ is an alkyl group having 1 to 10 carbon atoms, and anoptional unadjacent methylene group in the alkyl group may besubstituted by an oxygen atom or —CH═CH—, and an optional hydrogen atomin the alkyl group may be substituted by a fluorine atom; Y₁ is afluorine atom, a chlorine atom, OCF₃, OCF₂H, CF₃, CF₂H, CFH₂, OCF₂CF₂Hor OCF₂CFHCF₃; L₁₃ and L₁₄ are each independently a hydrogen atom or afluorine atom; Z₄ and Z₅ are each independently a 1,2-ethylene group, a1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, —CH═CH— or a single bond; aring D is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylenein which a hydrogen atom may be substituted by a halogen atom; and aring E is trans-1,4-cyclohexylene or 1,4-phenylene in which a hydrogenatom may be substituted by a fluorine atom; and at least one compoundselected from the group consisting of compounds of the following generalformulae (7), (8) and (9) as a third component

 wherein R₆ and R₇ is each independently an alkyl group having 1 to 10carbon atoms, and an optional unadjacent methylene group in the alkylgroup may be substituted by an oxygen atom or —CH═CH—, and an optionalhydrogen atom in the alkyl group may be substituted by a fluorine atom;rings I, J and 1< are each independently trans-1,4-cyclohexylene,pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may besubstituted by a fluorine atom; Z₇ and Z₈ are each independently —C≡C—,—COO—, —CH₂Cl—1₂—, —CH═CH— or a single bond.
 27. A liquid crystalcomposition which contains at least one of the liquid crystal compoundsdescribed in claim 1 as a first component, at least one compoundselected from the group consisting of compounds of the following generalformulae (5) and (6) as a second component

wherein R₄ and R₅ are each independently an alkyl group having 1 to 10carbon atoms, and an optional unadjacent methylene group in the alkylgroup may be substituted by an oxygen atom or —CH═CH—, and an optionalhydrogen atom in the alkyl group may be substituted by a fluorine atom;Y₂ is a —CN group or —C≡C—CN; a ring F is trans-1,4-cyclohexylene,1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; a ring G istrans-1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl in which ahydrogen atom may be substituted by a fluorine atom; a ring M istrans-1,4-cyclohexylene or 1,4-phenylene; Z₆ is a 1,2-ethylene group,—COO— or a single bond; L₁₅, L₁₆ and L₁₇ are each independently ahydrogen atom or a fluorine atom; and b, c and d are each independently0 or 1; and at least one compound selected from the group consisting ofcompounds of the following general formulae (7), (8) and (9) as a thirdcomponent

 wherein R₆ and R₇ is each independently an alkyl group having 1 to 10carbon atoms, and an optional unadjacent methylene group in the alkylgroup may be substituted by an oxygen atom or —CH═CH—, and an optionalhydrogen atom in the alkyl group may be substituted by a fluorine atom;rings, J and 1< are each independently trans-1,4-cyclohexylene,pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may besubstituted by a fluorine atom; Z₇ and Z₈ are each independently —C≡C—,—COO—, —CH₂Cl—1₂—, —CH═CH— or a single bond.
 28. A liquid crystalcomposition which contains at least one of the liquid crystal compoundsdescribed in claim 1 as a first component, at least one compoundselected from the group consisting of compounds of the following generalformulae (2), (3) and (4) as a second component

wherein R₃ is an alkyl group having 1 to 10 carbon atoms, and anoptional unadjacent methylene group in the alkyl group may besubstituted by an oxygen atom or —CH═CH—, and an optional hydrogen atomin the alkyl group may be substituted by a fluorine atom; Y₁ is afluorine atom, a chlorine atom, OCF₃, OCF₂H, CF₃, CF₂H, CFH₂, OCF₂CF₂Hor OCF₂CFHCF₃; L₁₃ and L₁₄ are each independently a hydrogen atom or afluorine atom; Z₄ and Z₅ are each independently a 1,2-ethylene group, a1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, —CH═CH— or a single bond; aring D is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylenein which a hydrogen atom may be substituted by a halogen atom; and aring E is trans-1,4-cyclohexylene or 1,4-phenylene in which a hydrogenatom may be substituted by a fluorine atom; at least one compoundselected from the group consisting of compounds of the following generalformulae (5) and (6) as a third component

 wherein R₄and R₅ are each independently an alkyl group having 1 to 10carbon atoms, and an optional unadjacent methylene group in the alkylgroup may be substituted by an oxygen atom or —CH═CH—, and an optionalhydrogen atom in the alkyl group may be substituted by a fluorine atom;Y₂ is a —CN group or —C═C—CN; a ring F is trans-1,4-cyclohexylene,1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; a ring G istrans-1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl in which ahydrogen atom may be substituted by a fluorine atom; a ring M istrans-1,4-cyclohexylene or 1,4-phenylene; Z₆ is a 1,2-ethylene group,—COO— or a single bond; L₁₅, L₁₆ and L₁₇ are each independently ahydrogen atom or a fluorine atom; and b, c and d are each independently0 or 1; and at least one compound selected from the group consisting ofcompounds of the general formulae (7), (8) and (9) as a fourth component

 wherein R₆ and R₇ is each independently an alkyl group having 1 to 10carbon atoms, and an optional unadjacent methylene group in the alkylgroup may be substituted by an oxygen atom or —CH═CH—, and an optionalhydrogen atom in the alkyl group may be substituted by a fluorine atom;rings, J and 1< are each independently trans-1,4-cyclohexylene,pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may besubstituted by a fluorine atom; Z₇ and Z₈ are each independently —C≡C—,—COO—, —CH₂Cl—1₂—, —CH═CH— or a single bond.
 29. A liquid crystalcomposition which comprises at least one fluorovinyl derivative compoundrepresent by the general formula (1)

wherein R₁ is an alkyl group having 1 to 18 carbon atoms, and amethylene group in the alkyl group may be substituted by an oxygen atom,a sulfur atom, —CH═CH— or —C≡C— and a hydrogen atom in the alkyl groupmay be substituted by a halogen atom or a cyano group; rings A, B and Care each independently 1,4-cyclohexylene, 1,4-cyclohexenylene,1,4-phenylene, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl orpyrimidine-2,5-diyl in which a hydrogen atom in the ring may besubstituted by a halogen atom; Z₁, Z₂ and Z₃ are each independently asingle bond, —CH₂CH₂—, —CH═CH—,-CH₂O, —OCH₂—, —(CH₂)₄—, —(CH₂)₃—O—,—O—(CH₂)₃—, —(CH₂)₂—CH═CH—, —CH═CH—(CH₂)_(2—, CF) ₂O—, OCF₂—, —CR₂═CH—,—CH═CR₂— or —CF═CF—, and R₂ is an alkyl group having 1 to 5 carbonatoms; X is a hydrogen atom or a fluorine atom; p and q are eachindependently 0 or 1; and m is an integer of O to 5; except for (1) acompound in which p is 0, q is 0, Z₃ is the single bond, —CH₂CH₂—,—CH₂O— or —OCH₂—, and the ring C is 1,4-cyclohexylene or 1,4-phenylene,(2) a compound in which p is 0, q is 1, Z₂ and Z₃are each the singlebond, the ring B is 1,4-phenylene, and the ring C is 1,4-cyclohexyleneor 1,4-phenylene, and (3) a compound in which p is 0, q is 1, Z₂ is asingle bond, Z₃ is —CH₂CH₂—, the ring B is 1,4-phenylene, the ring C is1,4-cyclohexylene, and X is a hydrogen atom; and at least one opticallyactive compound.
 30. A liquid crystal display device which comprises aliquid crystal composition which comprises at least one fluorovinylderivative compound repreby the general formula (1)

wherein R₁ is an alkyl group having 1 to 18 carbon atoms, and amethylene group in the alkyl group may be substituted by an oxygen atom,a sulfur atom, —CH═CH— or —C≡C— and a hydrogen atom in the alkyl groupmay be substituted by a halogen atom or a cyano group; rings A, B and Care each independently 1,4-cyclohexylene, 1,4-cyclohexenylene,1,4-phenylene, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl orpyrimidine-2,5-diyl in which a hydrogen atom in the ring may besubstituted by a halogen atom; Z₁, Z₂ and Z₃ are each independently asingle bond, —CH₂CH₂—, —CH═CH—, —CH₂O—, —OCH₂—, —(CH₂)₄—, —(CH₂)₃—O—,—O—(CH₂)₃—, —(CH₂)₂—CH═CH—, —CH═CH—(CH₂)₂—, CF₂O—, —OCF₂—, —CR₂═CH—,—CH═CR₂— or —CF═CF—, and R₂ is an alkyl group having 1 to 5 carbonatoms; X is a hydrogen atom or a fluorine atom; p and q are eachindependently 0 or 1; and m is an integer of 0 to 5; except for (1) acompound in which p is 0, q is 0, Z₃ is the single bond, —CH₂CH₂—,—CH₂O— or —OCH₂—, and the ring C is 1,4-cyclohexylene or 1,4-phenylene,(2) a compound in which p is 0, q is 1, Z₂ and Z₃are each the singlebond, the ring B is 1,4-phenylene, and the ring C is 1,4-cyclohexyleneor 1,4-phenylene, and (3) a compound in which p is 0, q is 1, Z₂ is asingle bond, Z₃ is —CH₂CH₂—, the ring B is 1,4-phenylene, the ring C is1,4-cyclohexylene, and X is a hydrogen atom; and at least one opticallyactive compound.